KR20070004518A - Water based concentrated product forms of light stabilizers made by a heterophase polymerization technique - Google Patents

Abstract

The instant invention pertains to a concentrated aqueous dispersion of organic light stabilizers with a particle size of less than 1000 nm, prepared by heterophase radical polymerization of ethylenically unsaturated monomers in the presence of the light stabilizers, wherein the weight ratio of light stabilizer to polymeric carrier is greater than 50/100. Another aspect of the invention is a process for the preparation of such aqueous dispersions with high light stabilizer content. Aqueous dispersions prepared according to this process are useful ingredients for adhesives, aqueous emulsions of natural or synthetic rubbers, water based inks or a water based coating compositions, which are consequently also subjects of the invention. ® KIPO & WIPO 2007

Description

Water based concentrated product forms of light stabilizers made by a heterophase polymerization technique

The present invention relates to a concentrated aqueous polymer dispersion having a particle size of less than 1000 nm prepared by heterophasic radical polymerization of ethylenically unsaturated monomers in the presence of a light stabilizer, in which case the weight ratio of the light stabilizer to polymer carrier is 100 Exceed 50 parts of unjust light stabilizer. Another aspect of the present invention relates to a method for preparing an aqueous dispersion using a high content of light stabilizer. Aqueous dispersions prepared according to the process of the present invention are useful materials for adhesives, aqueous emulsions of natural or synthetic rubbers, aqueous inks or aqueous coating compositions, which in turn is another object of the present invention.

Nonpolar light stabilizers, such as organic UV absorbers (UVAs) or hindered amine light stabilizers (HALS), are well known additives and are often used to protect coatings from degradation, especially against outdoor weathering. do. Paints or coatings in the field of need typically contain up to 5% by weight of organic light stabilizers, based on the total weight of the binder solids. However, unlike solvent-based coatings, in today's waterborne coatings, these light stabilizers are difficult to incorporate because a significant number of widely established nonpolar light stabilizers are insoluble and / or immiscible with aqueous coatings or paint compositions. Depending on the type of coating or paint composition and the type of light stabilizer, the creation of a stable homogeneous mixture may not be possible. In other cases, the initial homogeneous composition may show instability upon storage, resulting in separation of the light stabilizer and / or other components. Thus, undesired undesirable phenomena such as suspension, precipitation, serum formation, gelation and the like may appear. These phenomena due to the immiscibility of the light stabilizer are, for example, disadvantageous of coating performance. Therefore, various attempts have been made to solve the above-mentioned immiscibility problem.

Nonpolar light stabilizers, such as UV absorbers, are chemically modified into polar groups to improve water solubility / miscibility, thereby providing light stabilizer molecules with self-emulsifying properties in water. This approach has the disadvantage that chemical modifications are generally complex and expensive, and the behavior of polarly modified light stabilizers similar to surfactants can lead to environmental problems and can lead to cleaning and outdoor weathering of light stabilizers under wet conditions. Performance may be reduced.

At the stage of manufacturing the binder polymer, attempts have been made to pre-incorporate the light stabilizer into the binder polymer in order to achieve a uniform distribution of light stabilizers already present in the binder raw material. However, this approach is very unchangeable because the light stabilizer must not damage any process steps during the preparation of the binder polymer. The target amount of light stabilizer is already fixed with the binder polymer, and there is no freedom left to adjust or enhance the light stabilizer level during or after the formation of the paint. To include a wider range of coating compositions having different binders and various types and / or amounts of light stabilizers, an extended amount of light stabilizer modified binder resin may be needed. This is generally very unrealistic for paint manufacturers.

Non-polar light stabilizers can be prepared as concentrated aqueous emulsions or dispersions using emulsions or surfactants in relatively large amounts, typically 10-20% to active UVA. While such concentrated light stabilizer emulsions or dispersions can be used in different aqueous compositions, relatively large amounts of surfactants can impair moisture sensitivity or result in a lack of adhesion to the final coating material.

EP 0 942 037 describes a polymer phase containing polymer dispersion in which a polymer stabilizer is incorporated. Incorporation of the stabilizer is performed by swelling the final aqueous polymer dispersion in which the stabilizer is dissolved in an organic solvent. The polymerization step in the presence of the light stabilizer is not included. This approach is limited to certain light stabilizer / polymer blends, because not all light stabilizers readily penetrate into more or less swollen polymers.

Recent European Patent Publication No. 1 191 041 describes polymer dispersions prepared by radical miniemulsion polymerization of ethylenically unsaturated monomers in which dyes, UV absorbers or optical bleaches are dissolved. Radical miniemulsion polymerization is carried out in the presence of a nonionic surface active compound and an amphiphilic polymer. The amount of dye, UV absorber or optical bleach ranges from 0.5 to 50% by weight, based on the total weight of the final polymer matrix. The aqueous dispersions are useful as materials for the cosmetic field.

As mentioned above, the polymer dispersions described in EP 1 191 041 provide the desired additives in concentrations of 0.5 to 50% by weight, based on the total weight of the polymer matrix. In other words, polymers that do not affect the desired effect are present in much greater amounts than additives. For example, the UV absorber is present in less than 20% by weight, based on the monomer weight. While this may be acceptable in cosmetic compositions, the requirements in the fields of coatings, inks and plastics are different.

For example, the concentration of the light stabilizer provided as a carrier in the polymer matrix should be as high as possible in order to add as little as possible an undesired material that can adversely affect the weathering properties of the coating, ink or plastic composition.

It has been found that ethylenically unsaturated monomers can be heterophasic radically polymerized in the presence of a light stabilizer to produce concentrated aqueous polymer dispersions having a particle size of less than 1000 nm, in which case the weight ratio of the light stabilizer to polymer carrier is 100 Exceed 50 parts of unjust light stabilizer.

One aspect of the present invention provides a concentrated particle size of less than 1000 nm, comprising a polymer carrier (a) prepared by heterophasic radical polymerization of at least one ethylenically unsaturated monomer in the presence of a nonpolar organic light stabilizer (b). With respect to the aqueous polymer dispersion, the weight ratio of the nonpolar organic light stabilizer to the polymer carrier exceeds 50 parts of the nonpolar organic light stabilizer per 100 parts of the polymer carrier.

Any nonpolar, cationic or anionic surfactant may be added, preferably nonpolar or cationic surfactant.

Preferably, at least one ethylenically unsaturated monomer is used. When the polymerization is carried out using two or more ethylenically unsaturated monomers, the one or more ethylenically unsaturated monomers may be accompanied by two unsaturated functionalities to provide a certain level of crosslinking. For example, the amount of bifunctional monomer can vary from 0.5 to 20% by weight, based on the total weight of the monomer mixture.

Preference is given to concentrated aqueous polymer dispersions in which the weight ratio of the nonpolar organic light stabilizer to the polymer carrier is at least 80 parts, more preferably at least 100 parts, most preferably at least 10 parts per 100 parts of the polymer carrier.

In certain embodiments of the invention, the weight ratio of light stabilizer to polymer carrier is from 120 to 200 parts of light stabilizer per 100 parts of polymer carrier.

The average particle size is preferably less than 500 nm, more preferably less than 250 nm.

Droplet (oil / water emulsion) and particle (polymer dispersion) sizes were determined using dynamic lignt scattering (DLS) techniques, which are photo correlation spectroscopy (PCS) or quasi-elastic (QELS). also known as light scattering). As the measuring device, for example, an NICOMP particle size analyzer (NICOM model 380) (manufactured by Particle Sizing System, Santa Barbara, Calif.) Having a fixed scattering angle of 90 ° may be used. As a result of this measurement, the median diameter D _INT (INT: intensity weighted) can be measured.

For example, the total solids content of the concentrated aqueous polymer dispersion is at least 20% by weight, for example at least 30% by weight, preferably at least 40% by weight, based on the total weight of the aqueous dispersion. In a particularly preferred embodiment, the total solids content is at least 50% by weight, based on the total weight of the aqueous dispersion.

For example, a nonpolar organic light stabilizer is a group consisting of a hydroxyphenyl benzotriazole UV absorber, a hydroxyphenyl triazine UV absorber, a hydroxybenzophenone UV absorber, an oxalic acid aniline UV absorber, a sterically hindered amine light stabilizer and mixtures thereof Is selected from.

In a preferred embodiment, the water solubility of the nonpolar organic light stabilizer is less than 1% by weight, preferably less than 0.1% by weight and most preferably less than 0.01% by weight at room temperature and atmospheric pressure.

The proper balance of solubility in water and solubility in monomer droplets greatly affects the polymerization results. Therefore, the polarity of the nonpolar organic light stabilizer may be represented by "log p".

The partition coefficient log p (octanol / water) is, for example, a parameter widely used to assess the environmental impact of chemical compounds. The calculation of log p is described in W. M. Meylan, P. H. Howard, J. Pharmacentical Sciences 84, (1995), 83-92. In the context of the present invention, the log p value of the nonpolar organic light stabilizer is preferably at least 2.

For example, ethylenically unsaturated monomers include styrene, substituted styrenes, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl) acrylic anhydride, (alkyl) acrylic acid salts, ( Alkyl) acrylic acid esters, (alkyl) acrylonitrile, (alkyl) acrylamides, vinyl halides and vinylidene halides.

For example, ethylenically unsaturated monomers are of the formula CH ₂ = C (R _a )-(C = Z) -R _b {where Z is O or S, R _a is hydrogen or C ₁ -C ₄ alkyl, R _b is NH ₂ , O ⁻ (Me ⁺ ), glycidyl, unsubstituted C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₀₀ alkoxy, hydroxy substituted by one or more N and / or O atoms C ₁ -C ₁₈ alkoxy, unsubstituted C ₁ -C ₁₈ alkylamino, di (C ₁ -C ₁₈ alkyl) amino, hydroxy substituted C ₁ -C ₁₈ alkylamino or hydroxy substituted di (C _1- C ₁₈ alkyl) amino, —O—CH ₂ —CH ₂ —N (CH ₃ ) ₂ or —O—CH ₂ —CH ₂ —N ⁺ H (CH ₃ ) ₂ An ^— (where An ⁻ is a monovalent organic acid Or an anion of an inorganic acid, Me is a monovalent metal atom or ammonium ion.

Examples of specific ethylenically unsaturated monomers include styrene, iso-butyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, benzyl methacrylate, vinyl toluene, n-butyl acrylate, 3 Tert-butyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate or hydroxyethyl acrylate.

Particularly suitable monomer mixtures are mixtures of hydroxyethyl methacrylate, methylmethacrylate, cyclohexyl methacrylate, vinyl toluene, methyl methacrylate, iso-butyl methacrylate.

Examples of anionic AN ^- derived acids include C ₁ -C ₁₂ carboxylic acids, organic sulfonic acids such as CF ₃ SO ₃ H or CH ₃ SO ₃ H, mineral acids such as HCl, HBr or HI, Oxo acids such as HCl0 ₄ or complex acids such as HPFe or HBF ₄ .

(여기서, R_c는 C₁-C₂₅알킬, 페닐 또는 C₁-C₁₈알킬에 의해 치환된 페닐이고, R_d는 수소 또는 메틸이며, v는 1 내지 50의 정수이다)의 화합물이다. 이들 단량체는, 예를 들면, 상응하는 알콕시화 알콜 또는 페놀의 아실화에 의해 이온성 표면활성제로부터 유도된다. 반복 단위는 에틸렌 옥사이드, 프로필렌 옥사이드 또는 이들의 혼합물로부터 유도될 수 있다. Examples of R _a as C ₂ -C ₁₀₀ alkoxy blocked by one or more O atoms are

Wherein R _c is phenyl substituted by C ₁ -C ₂₅ alkyl, phenyl or C ₁ -C ₁₈ alkyl, R _d is hydrogen or methyl, and v is an integer from 1 to 50. These monomers are derived from ionic surfactants, for example by acylation of the corresponding alkoxylated alcohols or phenols. The repeat unit can be derived from ethylene oxide, propylene oxide or mixtures thereof.

또는

(여기서, R_a는 위에서 정의한 바와 같은 의미를 갖고, R_e는 메틸 또는 벤질이며, An^-는 바람직하게는 C1^-, Br^- 또는 ^-O₃S-CH₃이다)이다.Further examples of suitable acrylate or methacrylate monomers include

or

(Wherein, R _a has the same meaning as defined above, R _e is methyl or benzyl, An ^- is an O ₃ S-CH ₃ is preferably a C1 ^-, Br ^{- -,} or).

,

,

,

,

,

또는

가 있다.Additional acrylate monomers

,

,

,

,

,

or

There is.

,

,

,

또는

가 있다.Examples of suitable monomers other than acrylates include

,

,

,

or

There is.

Preferably, R _a is hydrogen or methyl, R _b is NH ₂ , glycidyl, unsubstituted or hydroxy substituted C ₁ -C ₄ alkoxy, unsubstituted C ₁ -C ₄ alkylamino, di (C _1- C ₄ alkyl) amino, hydroxy substituted C ₁ -C ₄ alkylamino or hydroxy substituted di (C ₁ -C ₄ alkyl) amino, Z is oxygen.

Acrylic esters and methacrylic esters are typically C ₁ -C ₁₈ alkyl esters.

Ethylenically unsaturated monomers are C ₁ -C ₁₈ acrylate, C ₁ -C ₁₈ methacrylate, acrylic acid, (meth) acrylic acid, styrene, vinyltoluene, hydroxy-functional acrylate or (meth) acrylate, alkoxylation Preference is given to concentrated aqueous polymer dispersions selected from the group consisting of acrylates or (meth) acrylates derived from alcohols, and polyfunctional acrylates or (meth) acrylates, and mixtures thereof.

Particularly useful methacrylates are iso-butyl methacrylate or cyclohexyl methacrylate.

In certain embodiments, the concentrated aqueous polymer dispersion is prepared from a mixture of at least two monomers as described above and at least one bifunctional monomer to obtain a crosslinked polymer. The amount of bifunctional monomer is, for example, 0.5 to 20% by weight, based on the total weight of the monomers.

Typical examples of difunctional monomers are divinyl-benzene, ethylene glycol diacrylate, butylene glycol diacrylate or diethylene glycol diacrylate.

The water solubility of the monomer or monomer mixture is preferably low, less than 5% by weight, more preferably less than 0.5% by weight, most preferably less than 0.1% by weight.

Preferably, in the concentrated aqueous polymer dispersion, hydroxybenzophenone is a compound of formula I, 2-hydroxyphenylbenzotriazole is a compound of formula IIa, IIb or IIc, and 2-hydroxyphenyltriazine is formula III And oxanilide is a compound of Formula IV.

In Formula I above,

v is an integer from 1 to 3,

w is 1 or 2,

Substituent Z is independently of each other hydrogen, halogen, hydroxyl or alkoxy having 1 to 12 carbon atoms.

In Formula IIa above,

의 라디칼{여기서, R ₄ 및 R ₅ 는, 서로 독립적으로, 탄소수 1 내지 5의 알킬이거나, R ₄ 는, 라디칼 C_nH_2n+1-m와 함께, 탄소수 5 내지 12의 사이클로알킬 라디칼을 형성하고, m은 1 또는 2이며, n은 2 내지 20의 정수이고, M은 화학식 -COOR₆의 라디칼(여기서, R ₆ 은 수소, 탄소수 1 내지 12의 알킬, 알킬 및 알콕시 잔기 중의 탄소수 1 내지 20의 알콕시알 킬, 또는 알킬 잔기 중의 탄소수 1 내지 4의 페닐알킬이다)이다}이고, R ₁ is hydrogen, alkyl having 1 to 24 carbon atoms, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, cycloalkyl having 5 to 8 carbon atoms, or

Radicals {where R ₄ And R ₅ , independently of one another, are alkyl of 1 to 5 carbon atoms, or R ₄ together with the radicals C _n H _{2n + 1-m} form a cycloalkyl radical of 5 to 12 carbon atoms, m is 1 or 2 And n is an integer from 2 to 20, and M is a radical of the formula -COOR ₆ , wherein R ₆ is hydrogen, alkyl of 1 to 12 carbon atoms, alkoxyalkyl of 1 to 20 carbon atoms, or alkyl in the alkoxy moiety Phenylalkyl having 1 to 4 carbon atoms in the residue),

R ₂ is hydrogen, halogen, alkyl having 1 to 18 carbons, and phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety,

R ₃ is hydrogen, chlorine, alkyl or alkoxy having 1 to 4 carbon atoms, or -COOR ₆ , wherein R ₆ is as defined above,

At least one of the radicals R ₁ and R ₂ is not hydrogen.

In Formula IIb above,

T is hydrogen or alkyl of 1 to 6 carbon atoms,

T ₁ is hydrogen, chlorine or alkyl or alkoxy having 1 to 4 carbon atoms,

n is 1 or 2,

의 라디칼{여기서, T ₃ 은 수소, 치환되지 않거나 1 내지 3개의 하이드록실 그룹 또는 -OCOT₆에 의해 치환된 탄소수 1 내지 18의 알킬, -O- 또는 -NT₆-에 의해 1회 또는 수 회 차단되며 치 환되지 않거나 하이드록실 또는 -OCOT₆에 의해 치환된 탄소수 3 내지 18의 알킬, 치환되지 않거나 하이드록실 및/또는 탄소수 1 내지 4의 알킬에 의해 치환된 탄소수 5 내지 12의 사이클로알킬, 치환되지 않거나 하이드록실에 의해 치환된 탄소수 2 내지 18의 알케닐, 알킬 잔기 중의 탄소수 1 내지 4의 페닐알킬이거나, 화학식 -CH₂CH(OH)-T₇ 또는

의 라디칼이고, T ₄ 및 T ₅ 는, 서로 독립적으로, 수소; 탄소수 1 내지 18의 알킬; -O- 또는 -NT₆-에 의해 1회 또는 수 회 차단된 탄소수 3 내지 18의 알킬, 탄소수 5 내지 12의 사이클로알킬, 페닐, 탄소수 1 내지 4의 알킬에 의해 치환된 페닐, 탄소수 3 내지 8의 알케닐, 알킬 잔기 중의 탄소수 1 내지 4의 페닐알킬, 또는 탄소수 2 내지 4의 하이드록시알킬(여기서, T ₆ 은 수소, 탄소수 1 내지 18의 알킬, 탄소수 5 내지 12의 사이클로알킬, 탄소수 3 내지 8의 알케닐, 페닐, 탄소수 1 내지 4의 알킬에 의해 치환된 페닐, 알킬 잔기 중의 탄소수 1 내지 4의 페닐알킬이고, T ₇ 은 수소, 탄소수 1 내지 18의 알킬, 치환되지 않거나 하이드록실에 의해 치환된 페닐, 알킬 잔기 중의 탄소수 1 내지 4의 페닐알킬, 또는 -CH₂OT₈이며, T ₈ 은 탄소수 1 내지 18의 알킬, 탄소수 3 내지 8의 알케닐, 탄소수 5 내지 10의 사이클로알킬, 페닐, 탄소수 1 내지 4의 알킬에 의해 치환된 페닐, 또는 알킬 잔기 중의 탄소수 1 내지 4의 페닐알킬이다)이다}이며, When n is 1, T ₂ is chlorine or the formula -OT ₃ or

Radicals wherein T ₃ is one or several times hydrogen, unsubstituted or substituted with 1 to 3 hydroxyl groups or alkyl having 1 to 18 carbon atoms, -O- or -NT ₆ -substituted by -OCOT ₆ Unsubstituted or substituted or substituted by hydroxyl or -OCOT ₆ alkyl having 3 to 18 carbon atoms, unsubstituted or substituted by hydroxyl and / or alkyl having 1 to 4 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, substituted Alkenyl having 2 to 18 carbon atoms or unsubstituted or substituted by hydroxyl, or phenylalkyl having 1 to 4 carbon atoms in the alkyl residue, or is of the formula -CH ₂ CH (OH) -T ₇ or

And T ₄ and T ₅ are independently of each other hydrogen; Alkyl having 1 to 18 carbon atoms; Alkyl having 3 to 18 carbons, interrupted once or several times by -O- or -NT _6- , cycloalkyl having 5 to 12 carbon atoms, phenyl, phenyl substituted by alkyl having 1 to 4 carbon atoms, 3 to 8 carbon atoms Alkenyl, phenylalkyl of 1 to 4 carbon atoms, or hydroxyalkyl of 2 to 4 carbon atoms, wherein T ₆ is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, or 3 to 3 carbon atoms Alkenyl of 8, phenyl, phenyl substituted by alkyl of 1 to 4 carbon atoms, phenylalkyl of 1 to 4 carbon atoms in the alkyl moiety, T ₇ is hydrogen, alkyl of 1 to 18 carbon atoms, unsubstituted or hydroxyl Substituted phenyl, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, or -CH ₂ OT ₈ , T ₈ is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, phenyl Substituted by alkyl having 1 to 4 carbon atoms Phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety),

또는 -O-T₉-O-의 라디칼{여기서, T ₆ 은 위에서 정의한 바와 같고, T ₁₀ 은 -O-에 의해 1회 또는 수 회 차단될 수 있는 탄소수 2 내지 20의 알킬렌 또는 사이클로헥실렌이며, T ₁₀ 과 T ₆ 은, 2개의 질소 원자와 함께, 피페라진 환이고, T ₉ 는 탄소수 2 내지 8의 알킬렌, 탄소수 4 내지 8의 알케닐렌, 탄소수 4의 알키닐렌, 사이클로헥실렌, -O-에 의해 1회 또는 수 회 차단된 탄소수 2 내지 8의 알킬렌이거나, 화학식 -CH₂CH(OH)CH₂0T₁₁OCH₂CH(OH)CH₂- 또는 -CH₂-C(CH₂0H)₂-CH₂-의 라디칼(여기서, T ₁₁ 은 탄소수 2 내지 8의 알킬렌, -O-에 의해 1회 또는 수 회 차단된 탄소수 2 내지 18의 알킬렌, 1,3-사이클로헥실렌, 1,4-사이클로헥실렌, 1,3-페닐렌 또는 1,4-페닐렌이다)이다}이다. When n is 2, T ₂ is a chemical formula

Or a radical of -OT ₉ -O- wherein T ₆ is as defined above and T ₁₀ is alkylene or cyclohexylene of 2 to 20 carbon atoms which may be blocked once or several times by -O-, T ₁₀ and T ₆ together with two nitrogen atoms are piperazine rings, T ₉ is alkylene having 2 to 8 carbon atoms, alkenylene having 4 to 8 carbon atoms, alkynylene having 4 carbon atoms, cyclohexylene, and -O. Alkylene of 2 to 8 carbon atoms blocked once or several times by-or -CH ₂ CH (OH) CH ₂ 0T ₁₁ OCH ₂ CH (OH) CH ₂ -or -CH ₂ -C (CH ₂ 0H ) ₂ -CH ₂ -radical, wherein T ₁₁ is alkylene having 2 to 8 carbon atoms, alkylene having 2 to 18 carbon atoms interrupted once or several times by -O-, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,3-phenylene or 1,4-phenylene).

In Formula IIc above,

R ' ₂ is C ₁ -C ₁₂ alkyl,

k is a number from 1 to 4.

In Formula III above,

u is 1 or 2,

r is an integer of 1 to 3,

Substituent Y ₁ is

Independently of each other, hydrogen, hydroxyl, phenyl or halogen, halogenomethyl, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 18 carbon atoms, or 1 to 18 carbon atoms substituted by -COO (C ₁ -C ₁₈ alkyl) Is alkoxy,

when u is 1, Y ₂ is alkyl having 1 to 18 carbon atoms; Phenyl unsubstituted or substituted by hydroxyl, halogen, alkyl or alkoxy having 1 to 18 carbon atoms; Substituted by -COOH, -COOY ₈ , -CONH ₂ , -CONHY ₉ , -CONY ₉ Y ₁₀ , -NH ₂ , -NHY ₉ , -NY ₉ Y ₁₀ , -NHCOY ₁₁ , -CN and / or -OCOY ₁₁ Alkyl having 1 to 12 carbon atoms; Alkyl of 4 to 20 carbon atoms, interrupted by one or more oxygen atoms, unsubstituted or substituted by hydroxyl or alkoxy having 1 to 12 carbon atoms; Alkenyl having 3 to 6 carbon atoms; Glycidyl; Cyclohexyl unsubstituted or substituted by hydroxyl, alkyl of 1 to 4 carbon atoms and / or -OCOY ₁₁ ; Phenylalkyl of 1 to 5 carbon atoms in the alkyl moiety which is unsubstituted or substituted by hydroxyl, chlorine and / or methyl, -COY ₁₂ or -SO ₂ Y ₁₃ , wherein Y ₈ is alkyl of 1 to 18 carbon atoms; Alkenyl having 3 to 18 carbon atoms; Alkyl of 3 to 20 carbon atoms interrupted by one or more oxygen atoms or sulfur atoms or -NT ₆ -and / or substituted by hydroxyl; Alkyl having 1 to 4 carbon atoms substituted by —P (O) (OY ₁₄ ) ₂ , —NY ₉ Y ₁₀ or —OCOY ₁₁ and / or hydroxyl, wherein Y ₁₄ is alkyl or phenyl having 1 to 12 carbon atoms ); Alkenyl having 3 to 18 carbon atoms; Glycidyl; Or phenylalkyl having 1 to 5 carbon atoms in the alkyl moiety, and Y ₉ and Y ₁₀ are independently of each other alkyl having 1 to 12 carbon atoms, alkoxyalkyl having 3 to 12 carbon atoms, dialkylaminoalkyl having 4 to 16 carbon atoms or carbon atoms; Cyclohexyl of 5 to 12, or Y ₉ and Y ₁₀ are in each case alkylene, oxaalkylidene or azaalkylidene of 3 to 9 carbon atoms, Y ₁₁ is alkyl of 1 to 18 carbon atoms, al to 2 to 18 carbon atoms Or is phenyl, Y ₁₂ is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, phenyl, alkoxy having 1 to 12 carbon atoms, phenoxy, alkylamino having 1 to 12 carbon atoms, or phenylamino, and Y ₁₃ is alkyl, phenyl having 1 to 18 carbon atoms, or alkylphenyl having 1 to 8 carbon atoms in the alkyl radical;

when u is 2, Y ₂ is interrupted by alkylene of 2 to 16 carbon atoms, alkenylene of 4 to 12 carbon atoms, xylylene, or one or more -O- and / or hydroxyl, -CH ₂ CH (OH ) CH ₂ -OY ₁₅ -OCH ₂ CH (OH) CH ₂ , -CO-Y ₁₆ -CO-, -CO-NH-Y ₁₇ -NH-CO- or-(CH ₂ ) _m -CO ₂ -Y ₁₈ Alkylene having 3 to 20 carbon atoms substituted by -OCO- (CH ₂ ) _m , wherein m is 1, 2 or 3, and Y ₁₅ is alkylene, phenylene or -phenylene- having 2 to 10 carbon atoms; M-phenylene-, wherein M is -O-, -S-, -S0 _2- , -CH ₂ -or -C (CH ₃ ) _2- ), and Y ₁₆ in each case is from 2 to 10 alkylidene, oxaalkylidene or thiaalkylidene; Phenylene; Or alkenylene having 2 to 6 carbon atoms, Y ₁₇ is alkylene having 2 to 10 carbon atoms; Phenylene; Or alkylphenylene having 2 to 11 carbon atoms in the alkyl residue, Y ₁₈ is alkylene having 2 to 10 carbon atoms; Or alkylene having 4 to 20 carbon atoms interrupted once or several times by oxygen.

In Formula IV above,

x is an integer from 1 to 3,

Substituents L , independently of each other, are hydrogen; In each case, alkyl, alkoxy or alkylthio having 1 to 22 carbon atoms; Phenoxy or phenylthio.

C ₁ -C ₁₈ alkyl may be straight or branched. Examples of alkyl having 18 or less carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl , 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethyl-hexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methyl undecyl, dodecyl, 1,1,3,3 , 5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.

의 라디칼{여기서, R₄ 및 R₅는, 각각 서로 독립적으로, 탄소수 1 내지 5의 알킬, 특히 메틸이거나, R₄는, C_nH_2n+1-m 라디칼과 함께, 탄소수 5 내지 12의 사이클로알킬 라디칼, 예를 들면, 사이클로헥실, 사이클로옥틸 및 사이클로데실을 형성하고, M은 화학식 -COOR₆의 라디칼(여기서, R₆은 수소; 및 알킬 및 알콕시 라디칼 중의 탄소수 1 내지 12의 알킬 또는 탄소수 1 내지 20의 알콕시알킬이다)}일 수 있다. 적합한 알킬 라디칼 R₆은 R₁에 관해 정의한 바와 같다. 적합한 알콕시알킬 그룹의 예에는 -C₂H₄0C₂H₅, -C₂H₄0C₈H₁₇ 및 -C₄H₈OC₄H₉가 있다. 탄소수 1 내지 4의 페닐알킬 때문에, R₆은, 예를 들면, 벤질, 쿠밀, α-메틸벤질 또는 페닐부틸이다. In the compounds of formula (IIa), R ₁ is hydrogen or alkyl having 1 to 24 carbon atoms, for example methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, tetradecyl, hexadecyl, octadecyl, nona Decyl and echosil, and may be corresponding side chain isomers. Further, in addition to phenylalkyl having 1 to 4 carbon atoms, such as benzyl, in the alkyl moiety, R ₁ is cycloalkyl having 5 to 8 carbon atoms, such as cyclopentyl, cyclohexyl and cyclooctyl, or

Radicals wherein R ₄ and R ₅ are each independently of each other an alkyl having 1 to 5 carbons, in particular methyl, or R ₄ together with a C _n H _{2n + 1-m} radical, Alkyl radicals such as cyclohexyl, cyclooctyl and cyclodecyl, and M is a radical of the formula -COOR ₆ , wherein R ₆ is hydrogen; and alkyl or alkoxy having 1 to 12 carbons in the alkyl and alkoxy radicals To alkoxyalkyl of 20). Suitable alkyl radicals R ₆ are as defined for R ₁ . Examples of suitable alkoxyalkyl groups are -C ₂ H ₄ 0C ₂ H ₅ , -C ₂ H ₄ 0C ₈ H ₁₇ and -C ₄ H ₈ OC ₄ H ₉ . Because of phenylalkyl having 1 to 4 carbon atoms, R ₆ is, for example, benzyl, cumyl, α-methylbenzyl or phenylbutyl.

In addition to hydrogen and halogen such as chlorine and bromine, R ₂ may be alkyl having 1 to 18 carbon atoms. Examples of such alkyl radicals are as defined for R ₁ . R ₂ may also be phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, for example benzyl, α-methylbenzyl and cumyl.

In all cases, halogen as substituent means fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, more preferably chlorine.

At least one of the radicals R ₁ and R ₂ must not be hydrogen.

In addition to hydrogen or chlorine, R ₃ may be alkyl or alkoxy having 1 to 4 carbon atoms, for example methyl, butyl, methoxy and ethoxy, and may be —COOR ₆ .

In formula (IIb), T is hydrogen or alkyl of 1 to 6 carbon atoms, such as methyl and butyl, and T ₁ is not only hydrogen or chlorine, but also alkyl or alkoxy of 1 to 4 carbon atoms, such as methyl, Methoxy and butoxy, when n is 1, T ₂ is chlorine or a radical of the formula -OT ₃ or -NT ₄ T ₅ . Here, T ₃ is as defined for hydrogen or alkyl having 1 to 18 carbon atoms, that is, R ₁ . These alkyl radicals may be substituted by 1 to 3 hydroxyl groups or radicals -OCOT ₆ . In addition, T ₃ is interrupted once or several times by -O- or -NT ₆ -and is unsubstituted or substituted by hydroxyl or -OCOT ₆ , as defined for alkyl having 3 to 18 carbon atoms, ie R ₁ . May be the same. Examples of T ₃ as cycloalkyl are cyclopentyl, cyclohexyl or cyclooctyl. In addition, T ₃ may be alkenyl having 2 to 18 carbon atoms.

의 라디칼일 수 있다.Suitable alkenyl radicals are derived from alkyl radicals as defined for R ₁ . These alkenyl radicals may be substituted by hydroxyl. Examples of T ₃ as phenylalkyl are benzyl, phenylethyl, cumyl, α-methylbenzyl or benzyl. In addition, T ₃ is represented by the formula -CH ₂ CH (OH) -T ₇ or

It may be a radical of.

Like T ₃ , T ₄ and T ₅ are, independently from each other, hydrogen; And alkyl having 1 to 18 carbons or alkyl having 3 to 18 carbons blocked once or several times by -O- or -NT _6- . In addition, T ₄ and T ₅ may be cycloalkyl having 5 to 12 carbon atoms, for example cyclopentyl, cyclohexyl and cyclooctyl. Examples of T ₄ and T ₅ as alkenyl groups can be found in the illustration of T ₃ . Examples of T ₄ and T ₅ as phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety are benzyl or phenylbutyl. Finally, these substituents may be hydroxyalkyl having 1 to 3 carbon atoms.

의 2가 라디칼이다. When n is 2, T ₂ is a chemical formula

Is a divalent radical.

In addition to hydrogen, T ₆ (as defined above) is alkyl, cycloalkyl, alkenyl, aryl or phenylalkyl, examples of such radicals already defined above.

In addition to the hydrogen and phenylalkyl radicals and long-chain alkyl radicals mentioned above, T ₇ is phenyl or hydroxyphenyl and -CH ₂ OT ₈ , where T ₈ is one of alkyl, alkenyl, cycloalkyl, aryl or phenylalkyl radicals. Can be).

The divalent radical T ₉ may be alkylene having 2 to 8 carbon atoms, which radical may be side chain. It may be added to alkenylene and alkynylene radicals T ₉ . In addition to cyclohexylene, T ₉ may be a radical of the formula -CH ₂ CH (OH) CH ₂ 0T ₁₁ OCH ₂ CH (OH) CH ₂ -or -CH ₂ -C (CH ₂ 0H) ₂ -CH _2-. have.

In addition, T ₁₀ is a divalent radical, and in addition to cyclohexylene, T ₁₀ is alkylidene having 2 to 20 carbon atoms which may be blocked once or several times by -O-. Suitable alkylene radicals are derived from alkyl radicals as defined for R ₁ .

In addition, T ₁₁ is an alkylidene radical. T ₁₁ has 2 to 8 carbon atoms or 4 to 10 carbon atoms when blocked once or several times by -O-. And T ₁₁ is 1,3-cyclohexylene, 1,4-cyclohexylene, 1,3-phenylene or 1,4-phenylene.

Together with two nitrogen atoms, T ₆ and T ₁₀ may be piperazine rings.

Examples of alkyl, alkoxy, phenylalkyl, alkylidene, alkenylene, alkoxyalkyl and cycloalkyl radicals and alkylthio, oxaalkylidene or azoalkylidene radicals in the compounds of formulas I, IIa, IIb, IIc, III and IV are It can be inferred from the description.

Benzotriazole UV absorbers according to formula (IIa) are generally preferred.

UV absorbers of formulas (I), (IIa), (IIb), (IIc), (III) and (IV) are well known per se, for example, WO 96/28431, EP 323 408, EP US Patent No. 57 160, US Patent No. 5,736, 597 (European Patent Publication No. 434 608), US Patent Publication No. 4 619 956, German Patent Publication No. 31 35 810 and British Patent Publication No. 1 336 391 Well described in the issue. Preferred meanings of substituents and respective compounds can be deduced from what has been described above.

Another embodiment of the hydroxyphenyl triazine-based UV absorbers is a compound of Formula IIIa.

In Formula IIIa above,

n is 1 or 2,

R ₃₀₁ , R ' ₃₀₁ , R ₃₀₂ and R' ₃₀₂ are each independently of the other H, OH, C ₁ -C ₁₂ alkyl; C ₂ -C ₆ alkenyl; C ₁ -C ₁₂ alkoxy; C ₂ -C ₁₈ alkenoxy; halogen; Trifluoromethyl; C ₇ -C ₁₁ phenylalkyl; Phenyl; Phenyl substituted by C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy or halogen; Phenoxy; Or phenoxy substituted by C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy or halogen,

R ₃₀₃ and R ₃₀₄ are each independently of the other H, C ₁ -C ₁₂ alkyl; OR '₃₀₇; C ₂ -C ₆ alkenyl; C ₂ -C ₁₈ alkenoxy; halogen; Trifluoromethyl; C ₇ -C ₁₁ phenylalkyl; Phenyl; Phenyl substituted by C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy or halogen; Phenoxy; Or phenoxy substituted by C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy or halogen,

R ₃₀₆ is hydrogen, C ₁ -C ₂₄ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₁₅ phenylalkyl,

When n is 1, R ₃₀₇ is, independently of each other, hydrogen or C ₁ -C ₁₈ alkyl, or R ₃₀₇ is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₈ alkoxy, allyloxy, halogen substituted by OH , -COOH, -COOR ₃₀₈ , -CONH ₂ , -CONHR ₃₀₉ , -CON (R ₃₀₉ ) (R ₃₁₀ ), -NH ₂ , -NHR ₃₀₉ , -N (R ₃₀₉ ) (R ₃₁₀ ), -NHCOR ₃₁₁ , -CN, -OCOR ₃₁₁ , phenoxy, and / or phenoxy substituted by C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy or halogen, or R ₃₀₇ is blocked by -O- and substituted by OH C ₃ -C ₅₀ alkyl, or R ₃₀₇ is C ₃ -C ₆ alkenyl; Glycidyl; C ₅ -C ₁₂ cycloalkyl substituted by OH, C ₁ -C ₄ alkyl or -OCOR ₃₁₁ ; C ₇ -C ₁₁ phenylalkyl unsubstituted or substituted by OH, Cl or CH ₃ ; -CO-R ₃₁₂ or -SO ₂ -R _313, or

이다when n is 2, R ₃₀₇ is C ₂ -C ₁₆ alkylidene, C ₄ -C ₁₂ alkenylene, xylylene, C ₃ -C ₂₀ alkylidene blocked by 0 and / or substituted by OH, or -CH ₂ CH (OH) CH ₂ OR ₃₂₀ -OCH ₂ CH (OH) CH _2- , -CO-R ₃₂₁ -CO-, -CO-NH-R ₃₂₂ -NH-CO- or-(CH ₂ ) _m -COO-R ₃₂₃ -OOC- (CH ₂ ) _m- , where m is an integer from 1 to 3, or

to be

Wherein R ₃₀₈ is C ₁ -C ₁₈ alkyl; C ₂ -C ₁₈ alkenyl; Hydroxyethyl; C ₃ -C ₅₀ alkyl blocked by O, NH, NR ₃₀₉ or S and / or substituted by OH; C ₁ -C ₄ alkyl substituted by —P (O) (OR ₃₁₄ ) ₂ , —N (R ₃₀₉ ) (R ₃₁₀ ) or —OCOR ₃₁₁ and / or OH; Glycidyl; C ₅ -C ₁₂ cycloalkyl; Phenyl; C ₇ -C ₁₄ alkylphenyl or C ₇ -C ₁₁ phenylalkyl,

R ₃₀₉ and R ₃₁₀ are, independently from each other, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkoxyalkyl, C ₄ -C ₁₆ dialkylaminoalkyl or C ₅ -C ₁₂ cycloalkyl, or R ₃₀₉ and R ₃₁₀ Together are C ₃ -C ₉ alkylene or -oxaalkylidene or -azaalkylidene,

R ₃₁₁ is C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl or phenyl, C ₂ -C ₁₂ hydroxyalkyl, cyclohexyl, or C ₃ -which may be interrupted by -O- and substituted by OH. C _5O alkyl,

R ₃₁₂ is C ₁ -C ₁₈ alkyl; C ₂ -C ₁₈ alkenyl; Phenyl; C ₁ -C ₁₈ alkoxy; C ₃ -C ₁₈ alkenyloxy; C ₃ -C ₅₀ alkoxy interrupted by O, NH, NR ₃₀₉ or S and / or substituted by OH; Cyclohexyloxy; C ₇ -C ₁₄ alkylphenoxy; C ₇ -C ₁₁ phenylalkoxy; Phenoxy; C ₁ -C ₁₂ alkylamino; Phenylamino; Tolylamino or naphthylamino,

R313 is C ₁ -C ₁₂ alkyl, phenyl, naphthyl or C ₇ -C ₁₄ alkylphenyl,

R314 is C ₁ -C ₁₂ alkyl, methylphenyl or phenyl,

R ₃₂₀ is C ₂ -C ₁₀ alkylidene, C ₄ -C _5O alkylidene blocked by O, phenylene or α-phenylene-X-phenylene- group, wherein X is -O-, -S- , -SO _2- , -CH ₂ -or -C (CH ₃ ) _2- ),

R ₃₂₁ is C ₂ -C ₁₀ alkylidene, C ₂ -C ₁₀ oxaalkylidene, C ₂ -C ₁₀ thiaalkylidene, C ₆ -C ₁₂ arylene or C ₁ -C ₆ alkenylene,

이고,R ₃₂₂ is C ₂ -C ₁₀ alkylidene, phenylene, tolylene, diphenylenemethane or

ego,

R ₃₂₃ is C ₂ -C ₁₀ alkylidene or C ₄ -C ₂₀ alkylidene blocked by O}.

In all cases, halogen is fluorine, chlorine, bromine or iodine.

Examples of alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3 -Dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethyl- Hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl and dodecyl.

Examples of alkoxy having 12 or less carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy and dodecyloxy There is.

Examples of alkenoxy are propenyloxy, butenoxy, pentenyloxy and hexenyloxy.

Examples of C ₅ -C ₁₂ cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclo-dodecyl. Preference is given to C ₅ -C ₈ cycloalkyl, in particular cyclohexyl.

C ₁ -C ₄ alkyl Substituted C ₅ -C ₁₂ cycloalkyls are, for example, methylcyclohexyl or dimethylcyclohexyl.

OH- and / or C ₁ -C ₁₀ alkyl substituted phenyls include, for example, methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl There is this.

Alkoxy substituted phenyls are, for example, methoxyphenyl dimethoxyphenyl or trimethoxyphenyl.

Examples of C ₇ -C ₉ phenylalkyl are benzyl and phenylethyl.

C ₇ -C ₉ phenylalkyl substituted in the phenyl radical by -OH and / or alkyl of up to 10 carbon atoms includes, for example, methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di Tert-butyl-4-hydroxybenzyl.

Examples of alkenyl are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom at position 1 is preferably saturated.

Examples of alkylene are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.

Examples of alkenylene are butenylene, pentenylene and hexenylene.

C ₆ -C ₁₂ arylene is preferably phenylene.

Alkyl blocked by O includes, for example, -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -O-CH ₃ -or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH _3- . Alkyl blocked by O is preferably derived from polyethylene glycol. Generally, it is a compound of the formula-((CH ₂ ) _a -O) _b -H / CH ₃ , where a is a number from 1 to 6 and b is a number from 2 to 10.

C ₂ -C ₁₀ oxaalkylidene and C ₂ -C ₁₀ thiaalkylidene can be deduced from the above-mentioned alkylene groups by substituting one or more carbon atoms with oxygen or sulfur atoms.

Specific examples of 2-hydroxybenzophenones include, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy and 2'- Hydroxy-4,4'-dimethoxy derivatives.

{여기서, R은 3'-3급-부틸-4'-하이드록시-5'-2H-벤조트리아졸-2-일페닐 또는 2-[2'-하이드록시-3'-(α,α-디메틸벤질)-5'-(1,1,3,3-테트라-메틸부틸)-페닐]벤조트리아졸이다}; 및 2-[2'-하이드록시-3'-(1,1,3,3-테트라메틸부틸)-5'-((α,α-디메틸벤질)-페닐] 벤조트리아졸이 있다.Specific examples of 2- (2'-hydroxyphenyl) benzotriazole include, for example, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'- Di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzo Triazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5'-tertiary -Butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl- 2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tertiary- Butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5'-[2- (2 Ethylhexyloxy) carbonylethyl] 2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5 -Chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tertiary -Butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'-[2- (2-ethylhexyloxy Carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzo-triazole, 2- (3'-3 Tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethyl Butyl) -6-benzotriazol-2-ylphenol]; 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzo Transesterification products of triazoles with polyethylene glycol 300;

{Where R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl or 2- [2'-hydroxy-3 '-(α, α- Dimethylbenzyl) -5 '-(1,1,3,3-tetra-methylbutyl) -phenyl] benzotriazole}; And 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-((α, α-dimethylbenzyl) -phenyl] benzotriazole.

Specific examples of 2- (2-hydroxyphenyl) -1,3,5-triazine include, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3 , 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4 -Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5- Triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyl Oxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy -Propyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / Tridecyloxy-2-hydroxypropoxy) -2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl-4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2- Hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1 , 3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine, 2 -(2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl -1-oxy) -2-hydroxy-propyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- (2-hydroxy-4- (2-ethyl-hexyl) oxy) phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine.

For example, hydroxyphenyl-triazine UV absorbers

,

,

(여기서, G₁은 CH(CH₃)-COO-C₂H₅이다),

(Wherein G ₁ is CH (CH ₃ ) —COO-C ₂ H ₅ ),

,

,

,

,

, R1, R2 및 R3가 CH(CH₃)-COO-C₈H₁₇이고 R4가 H인

및 R1, R2, R3 및 R4가 CH(CH₃)-COO-C₈H₁₇인

의 혼합물,R1 and R2 are CH (CH ₃ ) -COO-C ₈ H ₁₇ and R3 and R4 are H

, R1, R2 and R3 are CH (CH ₃ ) -COO-C ₈ H ₁₇ and R4 is H

And R 1, R 2, R 3 and R 4 are CH (CH ₃ ) —COO-C ₈ H ₁₇ .

Mixture of

,

,

,

,

,

,

,

,

,

,

또는

or

의 화합물이다.

Compound.

Hydroxyphenyl triazine UV absorbers are well known and partially commercially available items. These compounds can be prepared according to the literature as described above.

Specific examples of oxamides include, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di- Tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and 2-ethoxy-2'-ethyl-5,4'-di-tert- Mixture of butoxanilide, mixture of o-methoxy disubstituted oxanilide and p-methoxy disubstituted oxanilide, and o-ethoxy disubstituted oxanilide and p-ethoxy disubstituted oxanilide There is a mixture.

UV absorbers as mentioned above are mostly commercial items, for example Tinuvin® 109, 171, 326, 327, 328, 350, 360, 384, 400, manufactured by Ciba Specialty Chemicals, 405, 411 or Chimassorb® 81 or Cyasorb 1164 manufactured by Cytech Inc.

In many cases, it may be advantageous to use a combination of different kinds of UV absorbers, for example a combination of a benzophenone UV absorber and a benzotriazole UV absorber, or a combination of a hydroxyphenyltriazine UV absorber and a benzotriazole UV absorber. have. When using these formulations, the weight ratio of the two UV absorbers is for example 1: 5 to 5: 1, for example 1: 3 to 3: 1, in particular 1: 1.5 to 1.5: 1.

(여기서, R은 수소 또는 메틸이다)의 하나 이상의 라디칼을 함유한다. 본 발명에 유용한 입체 장애 아민 광 안정제는 바람직하게는 화학식 A-1 내지 A-10의 화합물 또는 화학식 B-1 내지 B-10의 화합물 이다(여기서, 화학식 B-8의 화합물은 화학식 B-8-a 및 B-8-b 중의 하나 이상의 화합물이다).Stereo hindered amines have the general formula

At least one radical of which R is hydrogen or methyl. The hindered amine light stabilizer useful in the present invention is preferably a compound of Formulas A-1 to A-10 or a compound of Formulas B-1 to B-10, wherein the compound of Formula B-8 is represented by Formula B-8- at least one compound of a and B-8-b).

In Formula A-1 above,

E ₁ is hydrogen, C ₁ -C ₈ alkyl, O, —OH, —CH ₂ CN, C ₁ -C ₁₈ alkoxy, C ₅ -C ₁₂ cycloalkoxy, C ₃ -C ₆ alkenyl, unsubstituted 1, C ₇ -C ₉ phenylalkyl substituted by 2 or 3 C ₁ -C ₄ alkyl; Or C ₁ -C ₈ acyl,

m ₁ is 1, 2 or 4,

when m ₁ is 1, E ₂ is C ₁ -C ₂₅ alkyl,

when m ₁ is 2, E ₂ is C ₁ -C ₁₄ alkylidene or a group of formula a-1,

when m ₁ is 4, E ₂ is C ₄ -C ₁₀ alcantetranil.

In the above formula a-1,

E ₃ is C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl,

E ₄ is C ₁ -C ₁₀ alkylidene,

E ₅ and E ₆ are each, independently of one another, C ₁ -C ₄ alkyl, cyclohexyl or methylcyclohexyl.

In Formula A-2,

Two of the radicals E ₇ are —COO— (C ₁ -C ₂₀ alkyl)

Two of the radicals E ₇ are groups of formula a-II.

In the above formula a-II,

E ₈ is _one of the definitions for E ₁ .

In Formula A-3 above,

E ₉ and E ₁₀ together form a C ₂ -C ₁₄ alkylidene,

E ₁₁ is hydrogen or a group of the formula -Z ₁ -COO-Z ₂ (Z ₁ is C ₂ -C ₁₄ alkylidene and Z ₂ is C ₁ -C ₂₄ alkyl),

E ₁₂ is _one of the definitions for E ₁ .

In Formula A-4 above,

The radicals E ₁₃ , each independently of one another, are one of those defined for E ₁ ,

The radicals E ₁₄ are each, independently of one another, hydrogen or C ₁ -C ₁₂ alkyl,

E ₁₅ is C ₁ -C ₁₀ alkylidene or C ₃ -C ₁₀ alkylidene.

In Formula A-5 above,

The radicals E ₁₆ , each independently of one another, are _one of the definitions for E ₁ .

In Formula A-6 above,

E ₁₇ is C ₁ -C ₂₄ alkyl,

E ₁₈ is _one of the definitions for E ₁ .

In Formula A-7 above,

E ₁₉ , E ₂₀ and E ₂₁ are each independently a group of the formula a-III.

In the above formula a-III,

E ₂₂ is _one of the definitions for E ₁ .

In Formula A-8 above,

The radicals E ₂₃ , each independently of one another, are one of those defined for E ₁ ,

E ₂₄ is hydrogen, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ alkoxy.

In Formula A-9 above,

m ₂ is 1, 2 or 3,

E ₂₅ is one of the things defined about E ₁ ,

이고,when m ₂ is 1, E ₂₆ is

ego,

when m ₂ is 2, E ₂₆ is C ₂ -C ₂ alkylidene,

When m ₂ is 3, E ₂₆ is a group of formula a-IV.

In the formula a-IV above,

The radicals E ₂₇ are each, independently of one another, C ₂ -C ₁₂ alkylidene,

The radicals E ₂₈ are each, independently of one another, C ₁ -C ₁₂ alkyl or C ₅ -C ₁₂ cycloalkyl.

In Formula A-10 above,

The radicals E ₂₉ , each independently of one another, are one of those defined for E ₁ ,

E ₃₀ is C ₂ -C ₂₂ alkylidene, C ₅ -C ₇ cycloalkylidene, C ₁ -C ₄ alkylidenedi (C ₅ -C ₇ cycloalkylidene), phenylene or phenylenedi (C ₁ -C ₄ Alkylidene).

In the above formula B-1,

R ₂₀₁ , R ₂₀₃ , R ₂₀₄ and R ₂₀₅ are each independently of the other hydrogen; C ₁ -C ₁₂ alkyl; C ₅ -C ₁₂ cycloalkyl; C ₁ -C ₄ -alkyl substituted C ₅ -C ₁₂ cycloalkyl; Phenyl; Phenyl substituted by -OH and / or C ₁ -C ₁₀ alkyl; C ₇ -C ₉ phenylalkyl; C ₇ -C ₉ phenylalkyl substituted by —OH and / or C ₁ -C ₁₀ alkyl on the phenyl radical; Or a group of formula bI,

R ₂₀₂ is C ₂ -C ₁₈ alkylidene, C ₅ -C ₇ cycloalkylidene or C ₁ -C ₄ alkylidenedi (B ₅ -C ₇ cycloalkylli, or

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ together with the nitrogen atom to which they are attached form a 5-10 membered heterocyclic ring, or

R ₂₀₄ and R ₂₀₅ together with the nitrogen atom to which they are attached form a 5-10 membered heterocyclic ring,

At least one of the radicals R ₂₀₁ , R ₂₀₃ , R ₂₀₄ and R ₂₀₅ is a group of formula bI.

In the above formula b-I,

R ₂₀₆ is hydrogen, C ₁ -C ₈ alkyl, O, —OH, —CH ₂ CN, C ₁ -C ₁₈ alkoxy, C ₅ -C ₁₂ cycloalkoxy, C ₃ -C ₆ alkenyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1,2 or 3 C ₁ -C ₄ alkyl on phenyl; Or C ₇ -C ₉ acyl,

b ₁ is a number from 2 to 50.

In the above formula B-2,

R ₂₀₇ and R ₂₁₁ are each, independently of one another, hydrogen or C ₁ -C ₁₂ alkyl,

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are each, independently of one another, C ₂ -C ₁₀ alkylidene,

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ and X ₈ are each independently a group of the formula b-II.

In the above formula b-II,

R ₂₁₂ is hydrogen; C ₁ -C ₁₂ alkyl; C ₅ -C ₁₂ cycloalkyl; C ₁ -C ₄ alkyl substituted C ₅ -C ₁₂ cycloalkyl; Phenyl; -OH- and / or C ₁ -C ₁₀ alkyl substituted phenyl; C ₇ -C ₉ phenylalkyl; C ₇ -C ₉ phenylalkyl substituted by —OH and / or C ₁ -C ₁₀ alkyl on the phenyl radical; As defined above with respect to formula (bI),

R ₂₁₃ is one of the definitions regarding R ₂₀₆ .

In Formula B-3 above,

R ₂₁₄ is C ₁ -C ₁₀ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl substituted C ₅ -C ₁₂ cycloalkyl, phenyl, or C ₁ -C ₁₀ alkyl substituted phenyl,

R ₂₁₅ is C ₃ -C ₁₀ alkylidene,

R ₂₁₆ is one of the things defined about R ₂₀₆ ,

b ₂ is a number from 2 to 50.

In Formula B-4 above,

R ₂₁₇ and R ₂₂₁ are each, independently of one another, a direct bond or a -N (X ₉ ) -CO-X ₁₀ -CO-N (X ₁₁ )-group, wherein X ₉ and X ₁₁ are each independently of one another; , Hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, C ₇ -C ₉ phenylalkyl or a group of formula bI, X ₁₀ is a direct bond or C 1 -C 4 alkylidene),

R ₂₁₈ is one of the things defined about R ₂₀₆ ,

R ₂₁₉ , R ₂₂₀ , R ₂₂₃ and R ₂₂₄ are each, independently of one another, hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl or phenyl,

R ₂₂₂ is hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, C ₇ -C ₉ phenylalkyl or a group of formula bl,

b ₃ is a number from 1 to 50.

In Formula B-5 above,

R ₂₂₅ , R ₂₂₆ , R ₂₂₇ , R ₂₂₈ and R ₂₂₉ are each, independently of one another, a direct bond or C ₁ -C ₁₀ alkylidene,

R ₂₃₀ is one of the things defined about R ₂₀₆ ,

b ₄ is a number from 1 to 50.

The compound of formula B-6 may be obtained by reacting a product obtained by the reaction of a polyamine of formula B-6-1 with cyanuric chloride with a compound of formula B-6-2.

In the above formula B-6-1 and formula B-6-2,

b'5, b "5 and b" '5 are the numbers of 2-12 each independently,

R ₂₃₁ is hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl or C ₇ -C ₉ phenylalkyl,

R ₂₃₂ is one of the definitions regarding R ₂₀₆ .

In Formula B-7 above,

A ₁ is hydrogen or C ₁ -C ₄ alkyl,

A ₂ is a direct bond or C ₁ -C ₁₀ alkylidene,

n ₁ is a number from 2 to 50.

In the above formula B-8-a and formula B-8-a,

n ₂ and n ₂ ^* are numbers from 2 to 50.

In Formula B-9 above,

A ₃ and A ₄ are each, independently of one another, hydrogen or C ₁ -C ₈ alkyl,

A ₃ and A ₄ together form a C 2 -C 14 alkylidene group,

n <_3> is a number of 1-50 each independently of each other.

In the above formula B-10,

n ₄ is a number from 2 to 50,

A ₅ is hydrogen or C ₁ -C ₄ alkyl,

The radicals A ₆ and A ₇ are each, independently of one another, C ₁ -C ₄ alkyl or a group of formula bl,

At least 50% of the radicals A ₇ are groups of the formula bl.

Examples of alkyl having 30 or less carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl , 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl , 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methyl undecyl, dodecyl, 1,1,3,3 , 5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, echosil, docosyl and triacentyl. As far as E ₁ , E ₈ , E ₁₂ , E ₁₃ , E ₁₆ , E ₁₈ , E ₂₂ , E ₂₃ , E ₂₅ , E ₂₉ , R ₂₀₆ , R ₂₁₃ , R ₂₁₆ , R ₂₁₈ , R ₂₃₀ and R ₂₃₂ One preferred definition is C ₁ -C ₄ alkyl, especially methyl. R ₂₃₁ is preferably butyl.

Examples of alkoxy having 18 or less carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy , Tetradecyloxy, hexadecyloxy and octadecyloxy. One preferred definition of E ₁ is octoxy. E ₂₄ is preferably C ₁ -C ₄ alkoxy and one preferred definition for R ₂₀₆ is propoxy.

Examples of C ₅ -C ₁₂ cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. Preference is given to C ₅ -C ₈ cycloalkyl, in particular cyclohexyl.

C ₁ -C ₄ alkyl Substituted C ₅ -C ₁₂ cycloalkyls are, for example, methylcyclohexyl or dimethylcyclohexyl.

C ₅ -C ₁₂ cycloalkoxy includes cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. Preference is given to C ₅ -C ₈ cycloalkoxy, in particular cyclopentoxy and cyclohexoxy.

-OH- and / or C ₁ -C ₁₀ alkyl substituted phenyls include, for example, methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or 3,5-di-tert-butyl-4-hydride Oxyphenyl.

C ₇ -C ₉ phenylalkyl includes benzyl and phenylethyl.

C ₇ -C ₉ phenylalkyl having up to 10 carbon atoms substituted by -OH and / or alkyl on the phenyl radical, for example, methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di Tert-butyl-4-hydroxybenzyl.

Examples of alkenyl having 10 or less carbon atoms include allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom at the 1 position is preferably saturated.

Examples of acyl having 8 or less carbon atoms include formyl, acetyl, propionyl, butyryl, pentanol, hexanol, heptanol, octanol, acryloyl, methacryloyl and benzoyl. Preferred are C ₁ -C ₈ alkanoyl, C ₃ -C ₈ alkenyl and benzoyl. Acetyl and acryloyl are particularly preferred.

Examples of alkylene having 22 or less carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.

가 있다.Examples of C ₃ -C ₁₀ alkylidene groups

There is.

Examples of C ₄ -C ₁₀ alkanetetrayl include 1,2,3,4-butanetetrayl.

An example of C ₅ -C ₇ cycloalkylidene is cyclohexylene.

An example of C ₁ -C ₄ alkylidenedi (C ₅ -C ₇ cycloalkylidene) is methylenedicyclohexylene.

Examples of phenylenedi (C ₁ -C ₄ alkylidene) are methylene-phenylene-methylene or ethylene-phenylene-ethylene.

또는

가 있다.When the radicals R ₂₀₁ , R ₂₀₂ and R ₂₀₃ together with the nitrogen atom to which they are bonded form a 5- to 10-membered heterocyclic ring, these rings are, for example,

or

There is.

Preferred are six membered heterocyclic rings.

When the radicals R ₂₀₄ and R ₂₅₃ together with the nitrogen atom to which they are attached form a 5-10 membered heterocyclic ring, these rings are, for example, 1-pyrrolidyl, piperidino, morpholi Furnace, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazinyl, 5,5,7-trimethyl-1-homopiperazinyl or 4,5,5,7-tetra Methyl-1-homopiperazinyl. Morpholino is particularly preferred.

One preferred definition of R ₂₁₉ and R ₂₂₃ is phenyl.

R ₂₂₆ is preferably a direct bond.

n ₁ , n ₂ , n ₂ ^* and n ₄ are preferably numbers from 2 to 25, in particular from 2 to 20.

n ₃ is preferably a number from 1 to 25, in particular from 1 to 20.

b ₁ and b ₂ are preferably numbers from 2 to 25, in particular from 2 to 20.

b ₃ and b ₄ are preferably numbers from 1 to 25, in particular from 1 to 20.

b ' ₅ and b "' ₅ are preferably 3, and b" ₅ is preferably 2.

The compounds described above are known in nature and are commercially available. These can all be manufactured by known methods.

Methods for preparing these compounds include, for example, U.S. Patent No. 5,679,733, U.S. Patent No. 3,640,928, U.S. Patent No. 4,198,334, U.S. Patent No. 5,204,473, U.S. Patent No. 4,619,958 US Patent Publication No. 4,110,306, US Patent Publication No. 4,110,334, US Patent Publication No. 4,689,416, US Patent Publication No. 4,408,051, US Patent Publication No. 768,175 (Derwent 88-138,751 / 20), U.S. Patent No. 5,049,604, U.S. Patent No. 4,769,457, U.S. Patent No. 4,356,307, U.S. Patent No. 4,619,956, U.S. Patent No. 5,182,390, U.S. Patent No. 2,269,819, U.S. Patent Publication No. 4,292,240, US Patent Publication No. 5,026,849, US Patent Publication No. 5,071,981, US Patent Publication No. 4,547,538, US Patent Publication No. 4,976,889, US Patent Publication US Patent No. 4,086,204, US Patent Publication No. 6,046,304, US Patent Publication No. 4,331,586, US Patent Publication No. 4,108,829, US Patent Publication No. 5,051,458, WO 94 / 12,544 (Derwent 94-177,274 / 22), US Patent Publication No. 262,439 (Derwent 89-122,983 / 17), US Patent Publication No. 4,857,595, US Patent Publication No. 4,529,760, US Patent Publication No. 4,477,615, CAS 136,504-96 -6, U.S. Patent No. 4,233,412, U.S. Patent No. 4,340,534, WO 98 / 51,690, and EP 1,803.

Compounds of formula B-6 are analogous to known methods, for example 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl, in the presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate. In an organic solvent such as an alcohol, the polyamine of formula B-6-1 is cyanuric chloride for 2 to 8 hours at -20 to + 10 ° C, preferably at -10 to + 10 ° C, especially 0 to + 10 ° C. After reacting with an acid at a weight ratio of 1: 2 to 1: 4, the reaction product may be prepared by reacting with 2,2,6,6-tetramethyl-4-piperidylamine of formula B-6-2. The molar ratio of 2,2,6,6-tetramethyl-4-piperidylamine to the polyamine of formula B-6-1 is, for example, 4: 1 to 8: 1. An amount of 2,2,6,6-tetramethyl-4-piperidylamine may be added in one fraction or more than one fraction at intervals of several hours.

The molar ratio of polyamine of formula B-6-1 to cyanuric chloride to 2,2,6,6-tetramethyl-4-piperidylamine of formula B-6-2 is preferably 1: 3: 5 To 1: 3: 6.

The preparation described below is one method of preparing the preferred product of formula B-6-a.

Preparation: stirring in 1,2-dichloroethane 250㎖, chlorinated cyanuric acid 23.6g (0.128mol), N, N'- bis [3-aminopropyl] ethylenediamine 7.43g (0.0426mol) and anhydrous potassium carbonate 18 g (0.13 mol) is reacted at 5 ° C. for 3 hours. The mixture is warmed for an additional 4 hours at room temperature. 27.2 g (0.128 mol) of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine are added and the resulting mixture is warmed at 60 ° C. for 2 hours. 18 g (0.13 mol) of anhydrous potassium carbonate were further added, and the mixture was further warmed at 60 ° C. for 6 hours. The solvent is distilled off under light vacuum (200 mbar) and replaced with xylene. 18.2 g (0.085 mol) of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine and 5.2 g (0.13 mol) of sodium hydroxide are added and the mixture is heated to reflux for 2 hours, It is further heated to reflux for 12 hours, and the water produced during the reaction is removed by azeotropic distillation. The mixture is filtered. The solution is washed with water and dried over Na ₂ SO ₄ . The solvent was evaporated and the residue was dried under vacuum (0.1 mbar) between 120 and 130 ° C. The dry product is obtained as a colorless resin.

In general, the product of formula B-6-a can be represented, for example, by a compound of formula B-6-α, B-6-β or B-6-γ. It may also be in the form of a mixture of these three compounds.

In the above formulas B-6-α, B-6-β and B-6-γ,

b ₅ is preferably 2 to 20, in particular 2 to 10.

Preferred compounds of formula B-6-α

이다.

to be.

Preferred compounds of formula B-6-β are

이다

to be

Preferred compounds of formula B-6- [gamma]

이다.

to be.

The hindered amine compound of component (c) is preferably commercially available DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN NOR 371 (RTM), TINUVIN 765 (RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM). ), TINUVIN 111 (RTM), TINUVIN 783 (RTM), TINUVIN 791 (RTM), MARK LA 52 (RTM), MARK LA 57 (RTM), MARK LA 62 (RTM), MARK LA 67 (RTM), HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM), SANDUVOR 3053 (RTM), SANDUVOR 3058 (RTM), DACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049 (RTM), SANDUVOR PR 31 (RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150 (RTM), GOODRITE UV 3159 (RTM), GOODRITE 3110 × 128 (RTM), UVINUL 4050 H (RTM), CHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM), CYASORB UV 3346 (RTM), CYASORB UV 3529 (RTM), DASTIB 1082 (RTM), CHIMASSORB 119 (RTM), UVASIL 299 (RTM), UVASIL 125 (RTM), UVASIL 2000 (RTM), UVINUL 5050 H (RTM), LICHTSCHUTZSTOFF UV 31 (RTM), LUCHEM HA B 18 (RTM), MARK LA 63 (RTM), MARK LA 68 (RTM), UVASORB HA 88 (RTM), TINUVIN 622 (RTM), HOSTAVIN N From the group consisting of 30 (RTM) and FERRO AM 806 (RTM) It is selected.

TINUVIN 770 (RTM), TINUVIN NOR 371 (RTM), TINUVIN 791 (RTM), TINUVIN 622 (RTM), TINUVIN 783 (RTM), CHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM), and CHIMASSORB 119 (RTM). desirable.

Most preferred are Tinuvin 770 (RTM), TUNIVIN 292 (RTM), TINUVIN 123 (RTM), TINUVIN 152 (RTM), TINUVIN NOR 371 (RTM) and TINUVIN 791 (RTM).

Formulas B-1, B-3, B-4, B-5, B-6-α, B-6-β, B-6-γ, B-7, B-8-a, B-8-b And the meaning of the terminal groups that saturate the free valences of the compounds of B-10 depend on their preparation. The terminal group may also be modified after preparation of the compound.

(여기서, X는, 예를 들면, 할로겐, 특히 염소이고, R₂₀₄ 및 R₂₀₅는 위에서 정의한 바와 같다)의 화합물을 화학식

(여기서, R₂₀₁, R₂₀₂ 및 R₂₀₃는 위에서 정의한 바와 같다)의 화합물과 반응시켜 화학식 B-1의 화합물을 제조하는 경우, 디아미노 라디칼에 결합된 말단 그룹은 수소 또는

이고, 트리아진 라디칼에 결합된 말단 그룹은 X 또는

이다.Chemical formula

Wherein X is, for example, halogen, in particular chlorine, and R ₂₀₄ and R ₂₀₅ are as defined above.

When reacting with a compound of formula (B), wherein R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are as defined above, to produce the compound of formula B-1, the terminal group bonded to the diamino radical is hydrogen or

And the terminal group bonded to the triazine radical is X or

to be.

When X is halogen, it is advantageous to replace X with, for example, -OH or an amino group if the reaction is a complete reaction. Examples of amino groups that may be mentioned include pyrrolidin-1-yl, morpholino, -NH ₂ , -N (C ₁ -C ₈ alkyl) ₂ and -NR (C ₁ -C ₈ alkyl), wherein R is hydrogen or a group of formula bI).

In addition, the compound of Formula B-1

의 화합물(여기서, R₂₀₁, R₂₀₂, R₂₀₃, R₂₀₄, R₂₀₅ 및 b₁은 위에서 정의한 바와 같고, R₂₀₄ ^*는 R₂₀₄에 관한 정의 중의 하나이며, R₂₀₅ ^*는 R₂₀₅에 관한 정의 중의 하나이다)이 포함된다.Chemical formula

Wherein R ₂₀₁ , R ₂₀₂ , R ₂₀₃ , R ₂₀₄ , R ₂₀₅ and b ₁ are as defined above, R ₂₀₄ ^* is one of the definitions for R ₂₀₄ , and R ₂₀₅ ^* is the definition for R ₂₀₅ It is one of).

One particularly preferred compound of formula B-1 is

이다.

to be.

Methods for preparing such compounds are described in the examples of US Pat. No. 6,046,304.

In the compound of the formula B-3, the end group bonded to the silicon atom is, for example, (R ₁₄ ) ₃ Si-O-, and the end group bonded to oxygen is, for example, -Si (R ₁₄ ). Can be _three .

In addition, when b ₂ is a number from 3 to 10, the compound of formula B-3 may be a cyclic compound, ie, the free valence shown in the formula structure forms a direct bond.

또는

이다.In the compound of Formula B-4, the terminal group bonded to the 2,5-dioxopyrrolidine ring is, for example, hydrogen, and the terminal group bonded to -C (R ₂₂₃ ) (R ₂₂₄ ) -radical, For example,

or

to be.

이고, 산소 라디칼에 결합된 말단 그룹은, 예를 들면,

이다.In the compound of the formula B-5, the terminal group bonded to the carbonyl radical is, for example,

And the terminal group bonded to the oxygen radical is, for example,

to be.

이고, 아미노 라디칼에 결합된 말단 그룹은, 예를 들면, 수소 또는

이다.In the compounds of the formulas B-6-α, B-6-β and B-6-γ, the terminal group bonded to the triazine radical is for example Cl or

And the terminal group bonded to the amino radical is for example hydrogen or

to be.

(여기서, A₁은 수소 또는 메틸이다)의 화합물을 화학식 Y-OOC-A₂-COO-Y(여기서, Y는, 예를 들면, 메틸, 에틸 또는 프로필이고, A₂는 위에서 정의한 바와 같다)의 디카복실산 디에스테르와 반응시켜 화학식 B-7의 화합물을 제조하는 경우, 2,2,6,6-테트라메틸-4-옥시피페리딘-1-일 라디칼에 결합된 말단 그룹은 수소 또는 -CO-A₂-COO-Y이고, 디아실 라디칼에 결합된 말단 그룹은 -O-Y 또는

이다.For example, the chemical formula

Wherein A ₁ is hydrogen or methyl, wherein the compound of formula Y-OOC-A ₂ -COO-Y, wherein Y is, for example, methyl, ethyl or propyl, and A ₂ is as defined above When reacting with a dicarboxylic acid diester of to produce the compound of formula B-7, the terminal group bonded to the 2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or- CO-A ₂ -COO-Y, and the terminal group bonded to the diacyl radical is -OY or

to be.

일 수 있다.In the compound of formula B-8-a, the terminal group bonded to the nitrogen may be, for example, hydrogen, and the terminal group bonded to the 2-hydroxypropylene radical may be, for example,

Can be.

In the compound of the formula B-8-b, the end group bonded to the dimethylene radical may be, for example, -OH, and the end group bonded to oxygen may be, for example, hydrogen. The terminal group can be a polyether radical.

In the compound of Formula B-10, the terminal group bonded to the —CH ₂ — moiety may be, for example, hydrogen, and the terminal group bonded to the —CH (CO ₂ A ₇ ) residue is, for example, − CH = CH-COOA ₇ may be.

의 화합물(여기서, n은 1 내지 15이다)이다.Specific examples of sterically hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate , Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) seva Kate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1- (2 -Hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensate, N, N'-bis (2,2,6,6-tetramethyl-4 Straight or cyclic condensates of -piperidyl) hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetra Methyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetrame Piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2 -(2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5 ] Decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis- (2,2,6,6-tetra Linear or cyclic condensates of methyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis ( Condensate of 4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2-chloro -4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-a Condensate of minopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] -decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-pipe Dill) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4 A mixture of -hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetramethyl-4-pi Condensed product of hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6 Condensation product of -trichloro-1,3,5-triazine with 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No. 136504-96-6), N- (2,2 , 6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecyl Succinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, 7,7,9,9 Tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4,5] decane and epichlorohydrin reaction product, 1,1-bis (1,2, 2,6,6-pentamethyl-4-piperi Oxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa Methylenediamine, diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- ( 2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin-copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine Reaction product, 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpy Ferridin-4-yl) -N-butyl-amino] -6- (2-hydroxyethyl) -amino-1,3,5-triazine, 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine, 5- (2-ethylhexanol) oxymethyl-3,3,5-trimethyl-2-morpholinone or Formulas as described in Example 2 of US Pat. No. 6,117,995

Is a compound wherein n is 1 to 15.

The sterically hindered amines mentioned above are well known and are mostly commercial items.

A further aspect of the present invention is the step of preparing at least one ethylenically unsaturated monomer by heterophasic radical polymerization in the presence of a nonpolar organic light stabilizer, wherein the nonpolar organic light stabilizer for the polymer carrier produced from the ethylenically unsaturated monomer is The weight ratio is greater than 50 parts of light stabilizer per 100 parts of polymer carrier), and a method for producing a concentrated aqueous polymer dispersion with an average particle size of less than 1000 nm.

In a particular embodiment of the invention, the process for preparing the concentrated aqueous polymer dispersion is

Dissolving, emulsifying or dispersing the nonpolar organic light stabilizer in at least one ethylenically unsaturated monomer (a),

(B) preparing a conventional oil-in-water emulsion consisting of a light stabilizer dissolved, emulsified or dispersed in at least one ethylenically unsaturated monomer,

(C) homogenizing a conventional emulsion into a miniemulsion having an average diameter of organic phase droplets of less than 1000 nm and

(D) polymerizing the miniemulsion by adding a polymerization initiator, wherein the weight ratio of the nonpolar organic light stabilizer to the polymer carrier produced from the ethylenically unsaturated monomer exceeds 50 parts of the light stabilizer per 100 parts of the polymer carrier.

In step (b), there is preferably further anionic, cationic or anionic surfactant.

Generally anionic and nonionic surfactants are preferred.

Optionally, other water miscible solvents may be present, generally less than 10% by weight, based on the water content. Examples of cosolvents useful in the present invention include aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkyl pyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids, and salts thereof , Esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, hydroxyether derivatives (e.g. butyl carbitol or cellosolve), amino alcohols, ketones, and the like, and derivatives thereof and mixtures thereof Can be. Specific examples include methanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran, and other water soluble or water miscible materials, and mixtures thereof.

Preference is given to water, water / alcohol mixtures, water / ethylene glycol or propylene glycol mixtures, water / acetone mixtures, water / tetrahydrofuran mixtures, or water / dimethylformamide mixtures.

Suitable surfactants or surface active compounds which can be added are known in the art. Typically used amounts are from 0.01 to 10% by weight, based on the total weight of the monomer (s).

Conventional surfactants useful in the present invention are nonionic, cationic or anionic surfactants.

Examples of anionic surfactants include alkyl or ammonium salts of C ₁₂ -C ₁₈ alkylsulfonic acids, succinic acids of ethoxylated alkanols or dialkyl esters of sulfuric acid half esters. These compounds are known, for example, from US Pat. No. 4,269,749 and are mostly commercial items, for example, the product Dowfax®2A1 (manufactured by Dow Chemical Company).

Nonionic surfactants include, for example, aliphatic or alicyclic compounds, for example ethoxylated phenols (mono, di, tri) having an ethoxylation degree of 3 to 50 and alkyl groups in the range of C ₄ -C ₉ , Ethoxylated long chain alcohols or polyethylene oxide / polypropylene oxide block copolymers.

In addition, protective colloids such as polyvinyl alcohol, starch, cellulose derivatives, or vinylpyrrolidone-containing copolymers can be added to produce a conventional oil-in-water emulsion according to step (b). Further examples are described in "Houben-Weyl, Methoden der Organischen Chemie, Band XIV / 1, Makromolekulare Stoffe, G. Thieme Verlag Stuttgart 1961, 411-420".

In general, the homogenization steps (b) and (c) are mechanically stirred (rotor / stator disperser) followed by a high force dispersion device, for example an ultrasonic device [see: J. Dispersion Sci. Technology 2002, 23 (1-3), 333-349] or a high pressure homogenizer (APV Gaulin homogenizer, Microfluidizer). Emulsification / homogenization can be carried out batchwise or continuously in the reaction mixture. Devices for this purpose are known in the art. Such matters are described, for example, in US Pat. No. 5,108,654.

The polymerization step (d) can be carried out by adding a free radical polymerization initiator.

The free radical initiator is preferably present in an amount of from 0.01 to 20% by weight, more preferably from 0.1 to 10% by weight and most preferably from 0.2 to 5% by weight, based on the total weight of the monomers or monomer mixture.

The polymerization initiator can be added to the reaction mixture batchwise or continuously.

Preferably, the free radical initiator of component (b) is a bis-azo compound, peroxide or hydroperoxide.

Specific preferred radical sources are 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methyl-butyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile ), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (isopart Tyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxy valeronitrile, dimethyl-2,2'-azobisisobutyrate, 2- (carbamoyl azo) isobutyronitrile, 2 , 2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (N, N'-dimethyleneisobutyramidine ), Free base or hydrogen chloride, 2,2'-azobis (2-amidinopropane), free base or hydrogen chloride, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxy Methyl) ethyl] propionamide} or 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide, ace Tyl cyclohexane sulfonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perfivalate, t-amyl perpivalate, bis ( 2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanol peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide , Diacetyl peroxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate, bis- (4-chlorobenzoyl) -peroxide, t-butyl perisobutyrate, t-butyl permaleinate , 1,1-bis (t-butylperoxy) 3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl Perisononoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butyl peracetate, t- Mill perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) propane, dicumyl peroxide, 2,5-dimethyl Hexane-2,5-di-t-butylperoxide, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, α, α'-bis (t-butylperoxy isopropyl) Benzene, 3,5-bis (t-butylperoxy) 3,5-dimethyl 1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexine-2,5-di-t- Butyl peroxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-mentane hydroperoxide, evacuation hydroperoxide, diisopropylbenzene mono-α -Hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

It is also possible to use combinations of Fe- or Co-compounds with peroxo salts or bissulphite salts or hydrosulfite salts. These blends are known as redox systems.

The polymerization temperature depends on the initiator used. Generally the polymerization temperature is in the range from 5 to 95 ° C, preferably 30 to 90 ° C. When pressurized, the temperature may rise to 120 ° C., but it is generally polymerized under atmospheric pressure.

Otherwise, polymerization can be initiated by photoinitiator and electromagnetic radiation, in particular actinic radiation.

Suitable photoinitiators for use in the method according to the invention are mainly any compounds and mixtures which form one or more free radicals upon electromagnetic radiation. Such photoinitiators include an initiator system consisting of a plurality of initiators and systems that each act independently or synergistically with each other. In addition to the public reagents such as amines, thiols, borates, enolates, phosphines, carboxylates and imidazoles, sensitive agents such as acridine, thiazene, coumarin, thioxanthone, tri It is also possible to use azine and dyes. Descriptions regarding such compounds and initiator systems are described, for example, in Crivello J. V., Dietliker K. K., (1999): Chemistry & Technology of UV & EB Formulation for Coatings, Inks &Paints; and Bradley G. (ed.) Vol. 3: Photoinitoator for free radical and Cationic Polymerization 2nd Edition, John Wiley & Son Ltd.

Suitable photoinitiators for step (b) of the process according to the invention may be unsaturated group containing initiators or unsaturated group free initiators. Such compounds and derivatives are, for example, benzoin, benzyl ketal, acetophenone, hydroxyalkylphenone, aminoalkylphenone, acylphosphine oxide, acylphosphine sulfide, acyloxyiminoketone, alkylamino substituted ketones, eg For example, Michler's ketone, peroxy compound, dinitrile compound, halogenated acetophenone, phenylglyoxylate, dimeric phenylglyoxalate, benzophenone, oxime, oxime ester, thioxanthone, coumarin, Derived from ferrocene, titanocene, onium salt, sulfonium salt, iodonium salt, diazonium salt, borate, triazine, bisimidazole, polysilane and dyes. It is also possible to use combinations of the abovementioned compounds with other compounds, and combinations of the abovementioned compounds with the corresponding open and / or sensitizing agents.

Surprisingly, it has been found that after the polymerization is completed, volatile components consisting mostly of water can be removed without aggregation of the particles. Thus, if necessary, the polymer particles can be easily redispersed.

Volatile components can be volatilized by standard methods such as spray drying.

As a result, another aspect of the present invention relates to a polymer powder obtainable by volatilizing the volatile components of the concentrated aqueous polymer dispersion as described above.

The highly concentrated light stabilizer-containing polymer powder can be used, for example, in the manufacture of powder coatings or in plastic articles in molding, blow molding or extrusion processing.

Further, the present invention is directed to degradation induced by heat, oxidation or light, comprising an organic material (a) susceptible to degradation induced by heat, oxidation or light and a concentrated aqueous polymer dispersion (b) as described above. To stabilized compositions.

For example, the organic material is a recording material.

For example, the recording material is a photographic material or an inkjet material.

In another aspect of the invention, the recording material is a concentrated aqueous polymer dispersion containing printing material in an overprint varnish.

The material stabilized with the novel polymer dispersion of the present invention is, for example, a recording material. Such materials are, for example, materials for photocopying and other copying techniques described in Research Disclosure 1990,31429 (pages 474-480).

Examples of recording materials include pressure-sensitive copier systems, microcapsule optical copier systems, thermal copier systems, photographic materials, and recording materials for inkjet printing.

The recording material is characterized by exceptional high quality, especially in terms of light stability of the material.

The recording material is known per se and has a structure corresponding to the use. The recording material consists of a substrate coated with one or more coatings, for example, paper or plastic film. Depending on the type of material, these coatings contain the required suitable components, for example silver halide emulsions, colorants, dyes and the like in the case of photographic materials. In particular, the recording material for inkjet printing contains a conventional substrate coated with an absorbing layer suitable for ink.

Similarly, uncoated paper is used for inkjet printing, in which case the paper simultaneously acts as a substrate and contains an absorbent for ink. In particular, materials suitable for inkjet printing are described in US Pat. No. 5,073,448, the disclosure of which is considered part of the context of the present invention.

In addition, the recording material may be transparent, for example in the case of a projection film.

The polymer dispersion may be incorporated into the recording material during paper production, for example by adding it to pulp. Another method of use is to spray the recording material or to add the recording material to the coating.

The coating for the transparent recording material for projection should not contain any light scattering particles, such as eye candy or filler.

The color binding coating may contain further additives such as antioxidants, light stabilizers, viscosity enhancers, brighteners, biocides and / or antistatic agents.

The coating is generally prepared as follows: The water soluble component, for example the binder, is dissolved in water and mixed. Solid components such as fillers and other additives as described above are dispersed in the aqueous medium. Advantageously, dispersions are prepared using devices such as ultrasonic devices, turbine stirrers, homogenizers, colloid mills, bead mills, sand mills, high speed stirrers and the like. A particularly advantageous matter of the polymer dispersion of the present invention is the ease of incorporation into the coating.

As mentioned, the field of use of recording materials is wide. The polymer dispersion can be used, for example, in a reduced pressure copier system. The polymer dispersion can be added to the paper to protect the microencapsulated dye precursor from light, and the polymer dispersion can be added to the binder of the developing layer to protect the dye formed therein.

Photosensitive microcapsule containing photocopier systems developed by pressure are particularly described in U.S. Patent Nos. 4,416,966, 4,483,912, 4,352,200, 4,535,050, 4,5365,463, 4,551,407, 4,562,137 and 4,608,330 number; And EP-A-139,479, 162,664, 164,931, 237,024, 237,025 and 260,129. In all such systems, polymer dispersions can be added to a color-accepting layer. Otherwise, a polymer dispersion can be added to the donor layer to protect the color former from light.

Furthermore, thermal or photosensitive diazonium salt; Oxidant-containing leuco dyes; Alternatively, when using Lewis acid-containing color lactones, the polymer dispersions can be used for optical recording materials based on photopolymerization, photosoftening or rupture of microcapsules.

The thermal recording material uses a color-imparting reaction between a colorless or lightly colored base dye and an organic or inorganic color developing agent to record an image produced by the heat-induced contact of the two materials. This type of thermal recording material is so widespread that it is used not only in recording media for fax and computer but also in many other fields, for example label printing.

The heat-sensitive recording material is made from the bottom to the base layer / thermal color-forming recording layer / optional protective layer / color-forming recording layer. The thermosensitive color-forming recording layer contains a color imparting compound and a color-developing compound as main components, and also contains a polymer dispersion according to the present invention. If a protective layer is present, the polymer dispersion may be incorporated into the protective layer.

The thermal recording material is described in, for example, Japanese Patent Laid-Open No. 8 267 915.

Further fields of use are recording materials for dye diffusion transfer printing, thermal wax transfer printing and dot matrix printing, and recording materials for use as electrostatic printers, electrographic printers, recorders or plotters. Among the recording materials mentioned, recording materials for dye diffusion transfer printers, for example, as described in EP 507,734, are preferred.

Polymeric dispersions can also be used in inks, preferably inks for inkjet printing, and are described, for example, in US Pat. No. 5,098,477, the disclosure of which is considered part of the context of the present invention. The ink, preferably the ink for inkjet printing, preferably contains water. The ink generally contains a polymer dispersion in a concentration of 0.01 to 20% by weight, in particular 0.5 to 10% by weight.

Examples of color photographic materials include color negative films, color reversal films, color positive films, color photo papers, color reversal photo papers, dye-color transfer materials for dye diffusion transfer printing or silver dye bleaching processes.

Examples of substrates suitable for color photographic materials include films and sheets made of semisynthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate; And paper in which a baryte layer or an α-olefin polymer layer (eg polyethylene) is laminated. These substrates can be colored with dyes or pigments, for example titanium dioxide. In addition, these base materials can also be colored black for the purpose of light blocking. The surface of the substrate is generally treated to improve adhesion of the photographic emulsion layer, such as corona discharge, and subsequently covering the base layer.

Preferably, the recording material comprises a silver halide emulsion layer starting from the substrate, among the blue sensitive layer, the green sensitive layer and the red sensitive layer. Among the color photographic materials, the polymer dispersion is preferably present in the layer above the green sensitive layer as described above, particularly preferably in the layer above the silver halide emulsion layer (s).

The polymer dispersion is preferably present in the photographic material in an amount of 0.1 to 10 g / m 2, for example 0.1 to 8 g / m 2, in particular 0.005 to 6 g / m 2, especially 0.01 to 4 g / m 2.

Photographic recording materials comprising a polymer dispersion in a layer above the silver halide emulsion layer (s) are generally preferred. Also,

Preferred is a photographic recording material comprising at least one red sensitive and green sensitive silver halide emulsion layer, with an intervening layer therebetween, wherein the at least one polymer dispersion of the present invention is an intercalation present between the red sensitive and green sensitive silver halide emulsion layers. Present in layers. Very particularly preferred photo recording materials comprise at least one red sensitive, green sensitive and blue sensitive silver halide emulsion layer and comprise at least two intercalating layers between the above mentioned layers and the protective layer, wherein at least one of the present invention The polymer dispersion is present in one or more layers above the one or more green sensitive silver halide emulsion layers, and the silver halide emulsion layer contains stabilizers and / or light stabilizers that require dark storage.

Essential components of the color photographic emulsion layer are a binder, silver halide particles and a coloring agent.

Of particular interest is, for example, one or more blue sensitive silver halide emulsion layers in which the color photographic recording material contains one or more yellow colorants, one or more green sensitive silver halide emulsion layers containing one or more magenta colorants, one or more cyan colorants. At least one red sensitive halogenation comprises an emulsion layer and conventional top layer (s) and insertion layer (s) in the substrate, wherein at least one layer comprises a polymer dispersion according to the invention.

The photographic emulsion can be spectralized using methine dyes or other dyes.

Particularly suitable dyes are cyanine dyes, and complex merocyanine dye containing mercrocyanine dyes.

An overview of polymethine dyes suitable as spectral sensitizers, suitable blends thereof and supersensitized blends is described in Research Disclosure 17643 (Dec. 1978), Chapter IV.

In differently sensitized emulsion layers, there are non-diffusion monomeric or polymeric colorants that can be located in the same layer or in adjacent layers. It is common for cyan colorants to be present in the red sensitive layer, magenta colorants to the green sensitive layer and yellow colorants to the blue sensitive layer.

Organic materials are adhesive and preference is given to aqueous emulsions, aqueous inks or aqueous coatings of natural or synthetic rubber.

In step (ii) there is preferably a nonionic, cationic or anionic surfactant.

Preferably the amount of component (b) is from 0.1 to 40% by weight, in particular from 0.1 to 20% by weight, in particular from 0.1 to 10% by weight, based on the weight of the solid component of component (a).

For very thin films, the amount of component (b) can be as high as 60% by weight, based on the solids content of component (a).

The adhesive is preferably polyurethane, polyacrylic, epoxy, phenol, polyimide, poly (vinyl butyral), polycyanoacrylate, polyacrylate, ethylene / acrylic acid copolymers and salts (isomers) thereof, silicon polymers, Poly (ethylene / vinyl acetate), attic polypropylene, styrene-diene copolymer, polyamide, hydroxyl terminated polybutadiene, polychloroprene, poly (vinyl acetate), carboxylated styrene / butadiene copolymer And poly (vinyl alcohol).

Aqueous emulsions of natural or synthetic rubbers are, for example, natural latexes or latexes of carboxylate styrene / butadiene copolymers.

The concentrated aqueous polymer dispersion can also be used in inks, preferably inks for inkjet printing.

If a water soluble, water miscible or water dispersible coating is desired, the ammonium salt of the acid group is present in the resin backbone.

The coating can be a physical drying system or a crosslinked polymer. For example, crosslinked polymers are derived from anhydrides on the one hand and from phenols, ureas and melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins. Dry and undried alkyd resins may also be used.

Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinkers, and their halogen-containing modified materials which are low flammable, can be used. Preference is given to acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates. Alkyd resins, polyester resins and acrylate resins are crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.

Crosslinked epoxy resins derived from polyepoxides can also be prepared, for example, from bisglycidyl ethers or cycloaliphatic diepoxides.

Alkyd resin lacquers are conventional stoving lacquers used especially for automotive coatings (car finishing lacquers), for example alkyd / melamine resins and alkyd / acrylic resins / melamine resins. See H. Wagner and Lacquer based on HF Sarx, "Lackkunstharze" (1977), pages 99-123. Other crosslinkers include glycouril resins, blocked isocyanates or epoxy resins.

Lacquers are particularly suitable for metal treatment coatings and solid form treatments, especially for retouching finishes, and are suitable for various coil coating applications. The lacquer stabilized with EK in the present invention is preferably coated by two conventional methods: single coating or double coating. In the latter case, the pigment-containing base coat is first coated and then the clear lacquer coat is coated thereon.

In addition, the coating material may be coated on the wood substrate to prevent discoloration of the wood.

The aqueous coating material may be based on a water soluble water softenable polymer or polymer dispersion. Substantially polar organic film formers having very high acid values, such as polyvinyl alcohol, polyacrylamide, polyethylene glycol, cellulose derivatives, acrylates and polyesters, are examples of water soluble polymers. Water-softening film formers consist of relatively short chain polymers containing acid or base groups, which can form salts incorporated into the side chains. The film former is neutralized with a suitable base or acid, which base or acid is evaporated during film formation to produce an insoluble polymer. Examples thereof include short oils and medium oil carboxylic acid alkyd resins, water-softening melamine resins, emulsifying epoxy resins or silicone-based emulsions. Several polymer types are used as water dilutable film formers. The most important of these are vinyl acetate copolymers with dibutyl maleate, vinyl esters of Versatic acid, acrylic ester acids, terpolymers with ethylene and vinyl chloride, vinyl propionate, polyacrylates And acrylate copolymers of pure acrylate, styrene and styrene-butadiene copolymers of polymethacrylate. The coating material may also be an aqueous radiation curable formulation consisting of a photopolymerizable compound.

In addition, the coating material may be further materials such as pigments or dyes, fillers, solvents as coalescing agents, accelerators for binders (curing agents), waxes or other hydrophobic agents, antifoams, homogenizers, wetting agents, rheology. Additives (thickeners or thixotropic agents), amines or bases for pH adjustment, photoinitiators, biocides, preservatives, fungicides or pesticides.

The coating material may be physically dried or chemically cured at room temperature by stoving or irradiation. The binder provided is a curable binder, which binder is generally used together with a curing agent and / or accelerator.

Any coating composition suitable for wood or wood based material coating can be used as the aqueous wood coating material. Examples of wood or wood based materials include furniture, parquets, window frames, panels, doors, wood core plywood, chipboard and fiberboard. Depending on their action or clarity, the wood coating material may be a primer / impregnated stain, a primer barrier stain, an outdoor topcoat such as Usstain, and an opaque coating. Presently preferred binders are straight chain acrylic dispersions, in many cases hybrid coatings as self-crosslinked acrylic dispersions or alkyd resin emulsions or mixtures thereof. For internal articles such as furniture and parquet, aqueous lacquers based mostly on self-crosslinking acrylic dispersions, polyurethane dispersions, acrylic polyurethane copolymer dispersions are preferably used. If film properties must meet high requirements, a two pack system consisting of an irradiation curable polymer dispersion or a hydroxyl-functional polymer dispersion and a water dispersible polyisocyanate is preferred.

Aqueous wood cladding materials may be applied to wood using conventional methods, such as impregnating, spreading, brushing, dipping, deluging, spraying or rollers or curtain machines. Can be covered. Impregnation under high pressure or vacuum is possible.

In general, compositions in which component (a) is an aqueous coating are preferred.

A particular aspect of the present invention is a powder coating comprising a solid binder material (a) stabilized against degradation induced by heat, oxidation or light and a light stabilizer containing polymer powder (b) as described above.

“Powder coating compositions” or “powder coatings” are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th, Completely Revised Edition, Vol. A 18, pages 438-444 (1991) in Section 3.4. same. By powder coating is meant a thermoplastic or bakeable crosslinkable polymer, which polymer is mainly applied to the metallic substrate in powder form. The manner of contacting the powder to the object to be coated is characterized by various coating techniques such as electrostatic powder spraying, electrostatic fluidized bed sintering, fixed bed sintering, fluidized bed sintering, rotary sintering or centrifugal sintering.

The organic film forming binder for the powder coating composition of the present invention is preferably, for example, an epoxy resin, polyester-hydroxyalkylamide, polyester-glycoluril, epoxy-polyester resin, polyester-triglycidyl iso Cyanurate, hydroxy-functional polyester-blocked polyisocyanate, hydroxy-functional polyester-uretdione, curing agent-containing acrylate resin, or a storage system based on a mixture of these resins .

Polyesters are generally hydroxy- or carboxy-functional and are generally prepared by condensation of diols with dicarboxylic acids. When polyols and / or polyacids are added to give branched polyesters, which are baked in the presence of a crosslinking agent, this creates a network structure, which structure has the desired physical properties, such as scratch resistance, impact on the coating. Gives strength and flexible strength. Instead of polyfunctional acids, anhydrides or acid chlorides such as acid anhydride, itaconic anhydride, phthalic anhydride, terephthalic anhydride, hexahydroterephthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, succinic anhydride and the like can be used. have. It is also possible to use a single ester, for example dimethyl terephthalate, in which case the polymerization is carried out by a transesterification reaction simultaneously with the removal of the volatile alcohol. Similarly, the method which can be performed is a method which combined the transesterification reaction and the condensation reaction. The polyester can also be prepared by polycondensation of hydroxycarboxylic acids such as 12-hydroxystearic acid and hydroxypivalic acid, or polycondensation of the corresponding lactones such as ε-caprolactone. have. Examples of dicarboxylic acids and polyacids include terephthalic acid, isophthalic acid, adipic acid, azelacic acid, sebacic acid, 1,12-dodecanedioic acid, pyromellitic acid, 3,6-dichlorophthalic acid, succinic acid, 1,3-cyclo Hexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of diols and polyols include ethylene glycol, propylene glycol, glycerol, hexanetriol, hexane-2,5-diol, hexane-1,6-diol, pentaerythritol, sorbitol, neopentyl glycol, trimethylol ethane, trimethylol Propane, tris-1,4-cyclohexanedimethanol, trimethylpentanediol, 2,2-diethyl-1,3-propane-diol, 2-methyl-2-butyl-1,3-propanediol, esterdiol 204 (Ester of hydroxypivalic acid and neopentyl glycol), hydrogenated bisphenol A, bisphenol A, hydroxypivalic acid, hydroxypivalate ester, 2-butyl-2-ethyl-1,3-propanediol, 1,4- Butanediol, 2-butene-1,4-diol, 2-butyne-1,4-diol or 2-methyl-1,3-propanediol.

Suitable crosslinkers for carboxy-functional polyesters include modifications by reaction with epoxy compounds such as Novolac®-epoxy resins, diglycidyl ethers of bisphenol A, hydrogenated bisphenol A, such as aliphatic dicarboxylic acids. Is bisphenol A. Suitable reactive epoxy compounds include, for example, triglycidyltriazolidine-3,5-dione, glycidyl esters of polyacids such as diglycidyl terephthalate and diglycidyl hexahydroterephthalate , Hydantoin epoxides (US Pat. No. 4,402,983), in particular triglycidyl isocyanurate, epoxidized unsaturated fatty acid esters (e.g., Uranox® from DSM) and Araldit®PT 910 [Ciba Spetch Alitatenhemie AG (manufactured by Ciba Spezialitatenchemie AG). Further crosslinkers for carboxy-functional polyesters include β-hydroxyalkylamides (US Pat. No. 4,076,917), for example Primid XL552, predominantly from adipic acid [Rohm & Haas]. ] Tetrafunctional β-hydroxyalkylamide derivatives. Derivatives of melamine, benzoguanimine and glycoluril alkylated with low molecular weight materials have also proven to be suitable. An example thereof is tetramethylmethoxyglycoluril (Powderlink® 1174 manufactured by American Cyanamid). Bisoxazolidines and trisoxazolidines such as 1,4-bisoxazolidinobenzene are also well known as crosslinkers.

Most recently, carboxy-functional polyesters which are capable of crosslinking with themselves because they contain chemically bound epoxy groups are known (Molhoek et al., 22nd Fatipec Con-gress, 15-19.5. 95, Budapest, Vol. 1,119-132].

Catalysts can be used in all systems in which epoxy groups or glycidyl radicals react with carboxyl groups or anhydrides. Examples thereof include, for example, amines or metal compounds such as aluminum acetylacetonate or tin octoate.

Polyisocyanate crosslinkers are particularly important as crosslinkers for hydroxy-functional polyesters. To prevent premature crosslinking due to the high reactivity of the isocyanate, the polyisocyanate is blocked (in the form of uretdione or as an adduct with the blocking agent) in order to obtain a well-balanced molten powder. . The most commonly used blocking agents are ε-caprolactam, methyl ethyl ketoxime or butanone oxime. Other suitable blocking agents for isocyanates are described in G.B. Guise, G.N. Freeland and G.C. Smith, "J. Applied Polymer Science", 23, 353 (1979); M. Bock and H. U. Maier-Westhues, "Progress in Product Development for Powder Coating Technology, XIX th Int. Conf. On Organic Coatings, Science and Technol., Athens, 12-16 July", 1993. Examples of blocked or unblocked polyisocyanates include 2-methylpentane 1,5-diisocyanate, 2-ethylbutane 1,4-diisocyanate, 3 (4) -isocyanatomethyl-1-methylcyclohexyl isocyanate, 3 Isocyanatomethyl-3,5,5-trimethylcyclohexane diisocyanate, tris (isocyanatomethyl) benzene, 4,4'-diisocyanatodicyclohexylmethane, 1,4-bis (isocyanato- Methyl) cyclohexane, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, especially isopron diisocyanate. For deblocking, it is common to add metallic catalysts such as tin octoate, dibutyltin oxide or dibutyltin dilaurate, for example polyisocyanate formulations.

Further crosslinkers suitable for hydroxy-functional polyesters are anhydrides such as trimellitic anhydride, and their reaction products with diols or diamines. Further examples of these crosslinkers are described in T. A. Misev, "Powder Coatings: Chemistry and Technology", J. Wiley & Sons, Chichester on pages 123-124.

Polyacrylates having hydroxyl, carboxyl or glycidyl functionality are also used as binders for powder coatings. These binders are prepared by conventional methods mainly from monomers such as styrene and straight or branched C ₁ -C ₈ alkyl esters of acrylic acid or methacrylic acid. In addition, other ethylenically unsaturated compounds such as divinylbenzene, acrylamide, methacrylamide, butoxymethylacrylamide, acrylonitrile, butadiene and the like can be added and copolymerized. Hydroxyls by copolymerization of hydroxy-functional monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate Achieve sensuality. For carboxyl functionality, ethylenically unsaturated acids and anhydrides are used, such as acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and maleic anhydride, itaconic anhydride, acrylic anhydride or methacrylic anhydride. US Patent Publication No. 3,836,604. Glycidyl functionality is imparted by copolymerization of monomers such as glycidyl acrylate and glycidyl methacrylate, as taught in EP 0,256,369 and US 3,876,578. do. As crosslinkers for polyacrylates having hydroxyl or carboxyl functionality, the same compounds as described for polyesters having hydroxyl or carboxyl functionality can be used. Further suitable crosslinkers include the epoxy compounds described in U.S. Patent No. 0,045,040. Suitable crosslinkers for polyacrylates having glycidyl functionality include dicarboxylic acids such as sebacic acid and 1,12-dodecanedicarboxylic acid, and anhydrides such as, for example, bistrimellitic anhydride, and the like. Compounds as described in publication 3,880,946. German Patent Publication No. 3 310 545 also describes self-crosslinking polyacrylates.

Epoxy resins for powder coatings generally include Novolac®-epoxy resins or, in particular, aromatic polyol-based epoxy resins, in particular bisphenol-based epoxy resins such as bisphenol A. Modified bisphenol epoxy resins described in Japanese Patent Application Laid-Open No. 58 187 464 (1982) are also known. Epoxy resins are used in solid aliphatic amines, solid aromatic amines, amine adducts, phenol resins, polyacids and crosslinkers from known carboxy-functional polyesters. Very particular mention of hardeners include dicyamides which are often used with catalysts, examples of which are Lewis acids, boron trifluoride-amine complexes, metal complexes, tertiary or quaternary amines, and imidazolines Derivatives such as 2-methylimidazoline.

A further aspect of the invention relates to a composition stabilized against degradation induced by heat, oxidation or light, comprising a thermoplastic polymer (a) and a polymer powder (b) as described above.

Thermoplastic polymers include, for example, polyolefins and all polymers known as engineering plastics, such as polyesters, polyamides, polystyrenes or polycarbonates.

A further aspect of the present invention is the use of concentrated aqueous polymer dispersions as described above as stabilizers against heat, oxidation or light induced degradation of organic materials susceptible to degradation induced from heat, oxidation or light; And the use of a polymer powder as described above as a stabilizer against heat, oxidation or degradation induced from light of the powder coating.

The preferences mentioned with regard to the concentrated aqueous polymer dispersion also apply to the stabilized composition and all other objects of the present invention.

As mentioned above, a composition stabilized against degradation induced by heat, oxidation or light may contain further additives such as plasticizers, lubricants, emulsifiers, pigments, optical brighteners, fire retardants or antistatic agents.

In addition, the compositions may contain light or heat stabilizers applied to conventional products. When additional UV absorbers or sterically hindered amines (HALS) are added, they can be selected from the above mentioned products.

Further additives are as follows.

1. Antioxidant

1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-3-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl 4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4 -Methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6- Di-tert-butyl-4-methoxymethylphenol, non-ylphenol linear or branched in the side chain, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1 '-Methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltri Deck-1'-yl) phenol and mixtures thereof.

1.2. Alkylthio methyl phenols, for example, 2,4-di-octyl thiomethyl -6-3-tert-butylphenol, 2,4-di-octyl-thio-6-methylphenol, 2,4-di-octyl thiomethyl - 6-ethylphenol, 2,6-di-dodecyl thiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert Amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl- 4-hydroxyphenyl) adipate.

1.4. Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylation Thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thio Bis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di- Secondary-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) -disulfide.

1.6. Alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylene Bis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tertiary -Butyl-phenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol ], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4, 4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis ( Tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1 , 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercap Tobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (tert-butyl-4-hydroxy-5-methyl-phenyl ) Dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1- Bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5 -Tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl Pentane.

1.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydride Roxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4- Hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxy- Benzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylation Malonates , for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl -4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) -2,4,6-trimethylbenzene, 1,4- Bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl -4-hydroxybenzyl) phenol.

1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6- Bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl- 4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzoyl) isocyanurate, 1,3 , 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris- (3,5-di-tert-butyl-4 -Hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) -hexahydro-1, 3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl Phosphonate, Dioctadecyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate And calcium salts of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.13. Mono alcohols or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propane Diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3- Containing thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, ester of β- (3,5-di-tert-butyl-4 -hydroxyphenyl ) propionic acid.

1.14. Mono alcohols or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propane Diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) oxamide, 3 Thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3, 9-bis [2- {3- (tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] An ester of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid containing undecane .

1.15. Mono alcohols or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, tee Odyethylene glycol, diethylene glycol, tri-ethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundanol, 3 Β- (3, containing thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane Ester of 5-dicyclohexyl-4-hydroxyphenyl) propionic acid.

1.16. Mono alcohols or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, tee Odyethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundanol, 3-thia 3,5-di-3 , containing pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane Esters of tert-butyl-4-hydroxyphenyl acetic acid.

1.17. Amides of β- (3,5-di-tert-butyl-4 -hydroxyphenyl ) propionic acid , for example N, N'-bis (3,5-di-tert-butyl-4-hydroxy Phenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) trimethylenediamide, N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl ] Propionyloxy) ethyl] oxamide (Naugard®XL-1 from Uniroyal)

1.18. Ascorbic acid (vitamin C)

1.19. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-tert-butyl-p-phenylenediamine, N, N'-bis ( 1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl)- p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p- Phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-tert-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4 -Tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine (eg, p, p'-di-tert-octyldiphenylamine), 4-n-butyl-aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'- Tetra-methyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-Dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylated tert-butyl / dialkylated tert-butyl tert-jade A mixture of tildiphenylamine, a mixture of monoalkylated nonyldiphenylamine / dialkylated nonyldiphenylamine, a mixture of monoalkylated dodecyldiphenylamine / dialkylated dodecyldiphenylamine, monoalkylated isopropyl / dialkylated isopropyl / isohexyl Mixtures of diphenylamine, monoalkylated tert-butyldiphenylamine / di Mixture of alkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, monoalkylated tert-butyl / dialkylated tertiary- A mixture of butyl tert-octylphenothiazine, a mixture of monoalkylated tert-octylphenothiazine / dialkylated tert-octylphenothiazine, N-allylphenothiazine, N, N, N ', N' -Tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetra-methylpiperid-4-yl-hexamethylenediamine, bis (2,2, 6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4- Come.

2. Metal deactivators such as N, N'-diphenyloxamide, N-salicyl-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N ' -Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalyl dihydra Zide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyldihydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl Dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

3. phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Erythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypenta Erythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, Tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-bipe Nylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2 , 4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8, 10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, 2,2 ', 2 "-nitrilo [triethyltris (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3', 5,5'-tetra- Tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy)- 1,3,2-dioxaphosphyran.

Particular preference is given to the following phosphites.

Tris (2,4-di-tert-butylphenyl) phosphite [Irgafos®168 manufactured by Ciba-Geigy], tris (nonylphenyl) phosphite,

(A),

(B),

(A),

(B),

(C),

(C),

(D),

(D),

(E)

(F) 및

(G)

(F) and

(G)

4. hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetedecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl -N-octadecylhydroxylamine, and N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

5. Nitrons such as N-benzyl-alpha-phenylnitron, N-ethyl-alpha-methylnitron, N-octyl-alpha-heptylnitron, N-lauryl-alpha-undecylnitrone , N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N N, N-dialkylhydrides derived from -octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, and hydrogenated taloamine Nitrons derived from loxylamines.

6. thio synergist (thiosynergist), for example, dilauryl thiodipropionate or Te us discharge reel thiodipropionate.

7. Peroxide Scavenger (scavenger), for example, esters of β- thiodiglycol acid, for example, lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or 2-mercapto-benzimidazole Zinc salt, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.

8. Polyamide stabilizers , for example copper salts in combination with salts of iodine and / or phosphorus compounds and divalent manganese.

9. Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes; Alkali metal salts and alkaline earth metal salts of higher fatty acids such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate .

10. nucleating agent (nucleating agent ) , for example, inorganic materials such as metal oxides such as talcum, titanium dioxide or magnesium oxide, phosphates, preferably carbonates or sulfates of alkaline earth metals; Monocarboxylic acids or polycarboxylic acids and salts thereof, such as organic compounds such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; And polymeric compounds such as ionic copolymers (ionomers). 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol and 1,3: 2,4-di ( Benzylidene) sorbitol is particularly preferred.

11. Fillers and reinforcements such as calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, wood flour, and Minutes or fibers of other natural products, synthetic fibers.

12. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, fire retardants, antistatic agents and blowing agents.

13, for benzofuran-one and indolinones, for example, those disclosed in U.S. Patent No. 4,325,863, 1 - No. 4,338,244, No. 5,175,312, 1 - 5,216,052 and No. 5,252,643 call; German Patent Publication Nos. 4 316 611, 4 316 622, and 4 316 876; Benzofuranone or indolinone, or 3- [4- (2-acetoxyethoxy) -phenyl] -5, described in European Patent Application Publication No. 0 589 839 or European Patent Publication No. 0 591 102. , 7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] -benzofuran-2- On, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-3 Tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2 -One, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzo-furan-2-one, 3- (3,4-dimethylphenyl)- 5,7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one.

In addition to the components as mentioned above, the coating compositions of the present invention are additives commonly used in paints and lacquers, such as slip agents, leveling agents, wetting agents, pigments, pigment dispersants, antifoams, matting agents. agents, waxes, anti skinning additives, adhesion promoters, in can stabilizers, coalescents, rheology modifiers, sag modifiers and thixotropic agents. Can be.

The following examples illustrate the invention.

General

Particle size distribution was measured by dynamic light scattering (DLS) (scattering angle 90 °) (Nicomp Model 380 manufactured by Particle Sizing System, Santa Barbara, CA). _Find (D _INT ) (INT: mean intensity diameter).

SONOPLUS HD 2200 (available on the market at BANDELIN electronic GmbH & Co. KG) [ultrasound converter UW 2200, booster horn SH 213 G and titanium flat tip ( flat tip) Ultrasonication is performed using generator GM 2200 with TT19). Typically, 500 ml of oil / water emulsion is treated for 3 minutes at 60% power.

The monomer is used without further purification.

A waterborne material of the following hydrophobic UV absorber is prepared.

  Compound 101 Compound 102

A. Manufacture Example

Example  A1

To prepare a stable oil / water emulsion, 20 g of compound 101 is dissolved in 20 g of methyl methacrylate (MMA), 1.6 g of stearyl methacrylate (SMA) and 0.06 g of butanedioldiacrylate (BDDA). The oil phase is added dropwise to a solution of 1.6 g sodium dodecyl sulfate in 56.5 g deionized water. After stirring for 30 minutes and sonicating, a dynamically stable emulsion with an average droplet size of less than 250 nm is obtained. The emulsion is heated up to 55 ° C. and a redox initiator (0.06 g ascorbic acid dissolved in 3 g deionized water; 0.25 ml H ₂ O ₂ (35%) diluted in 0.5 g deionized water) is subsequently added to the reaction mixture do. The reaction mixture is continued stirring with a mechanical stirrer, held at 55 ° C. for 3 hours, then cooled to room temperature and filtered through a 20 μm filter. The resulting particle size (DINT) is 141 nm. The content of active ingredient of compound 101 is 20% by weight, based on the total weight of the emulsion.

Example  A2

To prepare a stable oil / water emulsion, 24 g of compound 101 is dissolved in 16 g of methyl methacrylate (MMA), 1.6 g of stearyl methacrylate (SMA) and 0.05 g of butanedioldiacrylate (BDDA). The oil phase is added to a stirred solution of 1.6 g sodium dodecyl sulfate in 56.5 g deionized water. After stirring for 30 minutes and sonicating, a dynamically stable emulsion with an average droplet size of less than 250 nm is obtained. The emulsion is heated up to 55 ° C. and a redox initiator (0.08 g ascorbic acid dissolved in 3 g of deionized water; 0.32 mL of H ₂ O ₂ (35%) diluted in 0.5 g of deionized water) is subsequently added to the reaction mixture. do. The reaction mixture is continued stirring with a mechanical stirrer, held at 55 ° C. for 3 hours, then cooled to room temperature and filtered through a 20 μm filter. The resulting particle size (D _INT ) is 182 nm. The content of active ingredient of compound 101 is 24% by weight, based on the total weight of the emulsion.

Example  A3

To prepare a stable oil / water emulsion, 20 g of compound 101 is dissolved in 20 g of ethyl acrylate (EA), 1.6 g of stearyl methacrylate (SMA) and 0.06 g of butanedioldiacrylate (BDDA). The oil phase is added to a stirred solution of 1.6 g sodium dodecyl sulfate in 56.5 g deionized water. After stirring for 30 minutes and sonicating, a dynamically stable emulsion with an average droplet size of less than 250 nm is obtained. The emulsion is heated up to 55 ° C. and a redox initiator (0.06 g ascorbic acid dissolved in 3 g deionized water; 0.25 ml H ₂ O ₂ (35%) diluted in 0.5 g deionized water) is subsequently added to the reaction mixture do. The reaction mixture is continued stirring with a mechanical stirrer, held at 55 ° C. for 3 hours, then cooled to room temperature and filtered through a 20 μm filter. The resulting particle size (D _INT ) is 156 nm. The content of active ingredient of compound 101 is 20% by weight, based on the total weight of the emulsion.

Example  A4

To prepare a stable oil / water emulsion, 24 g of compound 101 are dissolved in 16 g ethyl acrylate (EA), 1.6 g stearyl methacrylate (SMA) and 0.05 g butanedioldiacrylate (BDDA). The oil phase is added to a stirred solution of 1.6 g sodium dodecyl sulfate in 56.5 g deionized water. After stirring for 30 minutes and sonication, a dynamically stable emulsion with an average droplet size of less than 250 nm is obtained. The emulsion is heated up to 55 ° C. and a redox initiator (0.08 g ascorbic acid dissolved in 3 g of deionized water; 0.32 mL of H ₂ O ₂ (35%) diluted in 0.5 g of deionized water) is subsequently added to the reaction mixture. do. The reaction mixture is continued stirring with a mechanical stirrer, held at 55 ° C. for 3 hours, then cooled to room temperature and filtered through a 20 μm filter. The resulting particle size (D _INT ) is 199 nm. The content of active ingredient of compound 101 is 24% by weight, based on the total weight of the emulsion.

Example  A5

To prepare a stable oil / water emulsion, 40 g of compound 101 is dissolved in 40 g of methyl methacrylate (MMA), 4.8 g of stearyl methacrylate (SMA) and 0.12 g of butanedioldiacrylate (BDDA). The oil phase was Disponil® FES 32 IS (31 wt.% Active) in 115 g of deionized water [Cognis Deutsche GmbH GmbH. Cage (manufactured by Cognis Deutschland GmbH & Co. KG) is added to 10.3 g of a stirred solution. After stirring for 30 minutes and sonicating, a dynamically stable emulsion with an average droplet size of less than 250 nm is obtained. The emulsion is heated up to 55 ° C. and a redox initiator (0.2 g of ascorbic acid dissolved in 3 g of deionized water; 0.81 ml of H ₂ O ₂ (35%) diluted in 2.0 g of deionized water) is subsequently added to the reaction mixture. do. The reaction mixture is continued stirring with a mechanical stirrer, held at 55 ° C. for 3 hours, then cooled to room temperature and filtered through a 20 μm filter. The resulting particle size (D _INT ) is 170 nm. The content of active ingredient of compound 101 is 20% by weight, based on the total weight of the emulsion.

Example  A6

Using a monomer mixture (mix I) containing 11% hydroxyethyl methacrylate, 15% vinyl toluol, 15% cyclohexyl methacrylate, 28% methyl methacrylate and 31% iso-butyl methacrylate The following samples were prepared. To prepare a stable oil / water emulsion, 40 g of compound 102 is dissolved in 40 g of Mix I, 3.2 g of stearyl methacrylate (SMA) and 0.12 g of butanedioldiacrylate (BDDA). The oil phase was added dropwise to 10.3 g of a stirred solution of Disponil® FES 32 IS (31 wt.% Active) (from Cognis Deutsche GmbH, Co. Cage) in 110 g of deionized water. After stirring for 30 minutes and sonicating, a dynamically stable emulsion with an average droplet size of less than 250 nm is obtained. The emulsion is heated up to 55 ° C. and a redox initiator (0.2 g ascorbic acid diluted in 5 g deionized water; 0.81 ml H ₂ O ₂ (35%) diluted in 5.0 g deionized water) is subsequently added to the reaction mixture. do. The reaction mixture is continuously stirred with a mechanical stirrer, held at 55 ° C. for 3 hours, then cooled to room temperature and filtered through a 20 μm filter. The resulting particle size (D _INT ) is 198 nm. The active ingredient content of compound 102 is 20% by weight, based on the total weight of the emulsion.

Example  A7

To prepare a stable oil / water emulsion, 40 g of compound 102 are dissolved in 40 g of mix I and 3.2 g of stearyl methacrylate (SMA). The oil phase is added to 10.3 g of a stirred solution of Disponil® FES 32 IS (31% by weight active) (from Cognis Deutsche GmbH, Co. Cage) in 110 g of deionized water. After stirring for 30 minutes and sonicating, a dynamically stable emulsion with an average droplet size of less than 250 nm is obtained. The emulsion is heated up to 55 ° C. and a redox initiator (0.2 g ascorbic acid dissolved in 5 g deionized water; 0.81 mL H ₂ O ₂ (35%) dissolved in 5.0 g deionized water) is subsequently added to the reaction mixture. do. The reaction mixture is continued stirring with a mechanical stirrer, held at 55 ° C. for 3 hours, then cooled to room temperature and filtered through a 20 μm filter. The resulting particle size (D _INT ) is 198 nm. The active ingredient content of compound 102 is 20% by weight, based on the total weight of the emulsion.

Example  A8

To prepare a stable oil / water emulsion, 40 g of compound 102 are dissolved in 40 g of Mix I and 3.2 g of stearyl methacrylate (SMA) and 0.06 g of dodecyl mercaptan (DDM). The oil phase is added to 10.3 g of a stirred solution of Disponil® FES 32 IS (31% by weight active) (from Cognis Deutsche GmbH, Co. Cage) in 110 g of deionized water. After stirring for 30 minutes and sonicating, a dynamically stable emulsion with an average droplet size of less than 250 nm is obtained. The emulsion is heated up to 55 ° C. and a redox initiator (0.2 g ascorbic acid dissolved in 5 g deionized water; 0.81 mL H ₂ O ₂ (35%) dissolved in 5.0 g deionized water) is subsequently added to the reaction mixture. do. The reaction mixture is continued stirring with a mechanical stirrer, held at 55 ° C. for 3 hours, then cooled to room temperature and filtered through a 20 μm filter. The resulting particle size (DINT) is 198 nm. The active ingredient content of compound 102 is 20% by weight, based on the total weight of the emulsion.

B. Cloth Example

Example  B1: Test of Light Stabilizers on Transparent Waterborne Penetrating Wood Coatings

The test composition is a commercially available aqueous wood coating which is imparted with water repellent properties to the coated wood due to the hydrophobic component of the coating (Prophyconazole-containing Woodcare QS from Bohme, Switzerland, containing about 12% solids). . Different UV absorber products are added to the test composition with stirring for 2 hours. The homogeneity of the composition is evaluated at different time intervals in a closed bottle at room temperature to assess the storage stability of the fully formed paint (see Table 1). In addition, untreated paint was coated on fir wood panels (once with a brush) and accelerated weathering equipment (QUV Tester: UV-A 340 nm manufactured by Q Panel Company). Fluorescent lamp, test cycle 5 hours, exposure at 58 ° C. for 1 hour, dark water spray 22 ° C.].

LIGNOSTAB®1198 is a sterically hindered amine commercially available from Ciba Specialty Chemicals and is used to prevent lignin degradation associated with UV absorbers.

Tinuvin® 1130 is a UV absorber commercially available from Ciba Specialty Chemicals.

Example  B2: transparent aqueous ( waterborne ) Testing of Light Stabilizers on Film Forming Wood Coatings

As the test composition, a transparent waterborne wood coating based on an acrylic dispersion having the following composition was used (solids content about 43% by weight).

Neocryl®XK 90 (manufactured by NeoResins) 91.2 parts

4.7 parts water

Ethyl diglycol 3.4 parts

Borchigel® L75 N (manufactured by Borchers) / water (1/1) 0.4 part

Dehydran® 1293 [manufactured by Cognis] 0.3 parts

100.0 copies in total

The additives listed in Table 2 are added to the composition with stirring for 2 hours. The composition is coated with a brush on a panel of fir wood. Each coat was dried for one day (a coat amount of about 100 g / m 2), and a total of three coats were applied. The homogeneity of the composition is evaluated at different time intervals in a closed bottle at room temperature to assess the storage stability of the fully formed paint. Coated fir wood panels are tested on an accelerated weathering instrument (QUV Tester manufactured by Q Panel Company: UV-A 340 nm fluorescent lamp, test cycle 5 hours, exposure at 58 ° C. for 1 hour, dark water spray 22 ° C.). Weathering performance is assessed by the color change of the wood relative to the original wood color (before exposure) and the start of crack formation examined under the microscope.

Table 2 shows that the products according to the invention not only have good miscibility and good compositional stability, but also the weather resistance performance is significantly improved (extended durability) in most cases.

Example  B3: Testing of Light Stabilizers in Slightly Colored, Waterborne Penetrating Wood Coatings

A commercially available product from Behr (USA) (Deckplus wood-coloured waterproofing wood finish, naturally transparent) is used as the coating system. Different UV absorber products are added to the composition with stirring for 2 hours. The composition was coated on a fir wood panel once and accelerated weatherproof equipment [QUV Tester manufactured by Q Panel Company: UV-A 340 nm fluorescent lamp, test cycle 5 hours, exposure at 58 ° C. for 1 hour, dark water spray 22 ° C. ]. Weathering performance is evaluated by visually identifying the extent of wood aging due to lignin degradation. Further use of LIGNOSTAB 1198 improves wood stability. The product tested showed no negative effect on the storage stability of the composition.

The product according to the invention has an increased lifetime despite the low throughput of the active ingredient of the composition joule.

Example  B4: Test of Light Stabilizers for Waterborne 1p and 2p Acrylic Acid / Isocyanate Industrial Coatings

In aqueous 1-pack acrylic acid / blocked polyisocyanate and two different aqueous 2-pack acrylic / polyisocyanate coating compositions, the light stabilizer products of Examples A6, A7 and A8 are tested in comparison to Tinuvin 1130.

Light stabilizers (Tin 292 1% and active UVA 2%; these contents are based on the total content of the binder solids of the paint system) are added to the fully prepared paint, homogeneous incorporation, storage stability at room temperature and 40 ° C., Pot-life (for 2p compositions) and durability (UVCON and CAM 180 exposure) were tested.

For 2p compositions, storage stability is tested in the corresponding composition without the hardener component. As always, comparisons are made using the composition without the light stabilizer.

Test 4.1: Light Stabilizer Composition in Aqueous 1p Composition ( Joncryl  Binder)

Test 4.2: Light Stabilizer Composition in Aqueous 2p Composition ( Macrynal  Binder)

Test 4.3: Light Stabilizer Composition in Aqueous 2p Composition ( Setalux  Binder)

In all the tests of Tables 4.1, 4.2 and 4.3, the products of Examples A6, A7 and A8 can be easily and uniformly incorporated into the paint by simply mixing with Tin 1130 in the same manner as the Comparative Examples. In contrast, Compound 102, which is UVA used in CG43-0365, CG43-0366 and CG43-0367 products, cannot be mixed uniformly in these compositions.

After 4 weeks of storage at room temperature and 40 ° C., all test paints, including the control group without LS, showed no immiscibility (ie, the viscosity did not decrease or exceeded 20% of the original value).

Test 4.4: Storage stability test measuring the viscosity of the composition after storing the composition of Table 4.2 for 4 weeks

Test 4.5: Storage stability test measuring the viscosity of the composition after storing the composition of Table 4.3 for 4 weeks

The paint composition (without hardener) does not significantly increase in viscosity during storage (see Tables 4.4 and 4.5). This demonstrates that the new product does not impart storage stability to the 2p paint composition.

Test 4.6: Appearance of paint film according to composition 4.3

The general appearance properties of the cured projecting coating do not change in the presence of the UVA product according to Examples A6, A8 and A8.

Test 4.7: Composition of Table 4.2 UVCON  Durability test

Test 4.8: of the composition of Table 4.3 UVCON  Durability test

Compared to the unstabilized sample and Tinuvin® 1130 (= Tin 1133), the increase in ΔE ^* value under accelerated exposure is significantly reduced when using the products of Examples A6, A8 and A8. In addition, the gloss retention is improved when the paint is stabilized with the product according to the invention.

C. Inkjet Application example

Example C1

Using a HP 970Cxi, Lexmark Z65, Canon BJC 8200, and Epson Stylus 890 inkjet printer, a gelatinous coating consisting of the following composition is coated on a swellable and nanoporous inkjet photo paper with a cyan, magenta and yellow step image.

Ingredient: Content (/ ㎡)

Gelatin 1200mg

Wetting agent 100mg

300 mg of product of Example 1 (active)

After drying the top coat, the overcoat prints were irradiated on an Atlas C1-35 weather resistant instrument and the light resistance of the prints protected by a control coating (containing no UV absorbers) Evaluate and compare. Regardless of the ink system or print media, CGL 362 containing overcoat reliably protects the photo fade of the print compared to the control coating.

D. Photos Example

Example D1 : Incorporation into gelatin layer and UV  Act as an absorbent

A gelatin coating composed of the following compositions is coated on a polyester substrate in a conventional manner. The polymer dispersion of Example A1 is incorporated into the gelatin casting solution under gentle mixing (emulsification step is unnecessary).

Ingredient: Content (/ ㎡)

Gelatin 1200mg

Wetting agent 100mg

320 mg of product of Example 1 (active)

The curing agent is the potassium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine. Wetting agent is sodium 4,8-diisobutylniphthalene-2-sulfonate.

The gelatinous coating is dried at 20 ° C. for 2 days.

A transparent UV absorbing layer is obtained which is suitable for photographic recording materials, for example UV filter coatings.

The UV absorption spectrum of the UV absorbing layer is recorded using a Perkin Elmer Lambda 15 spectrometer. The maximum absorption wavelength (λ _max ) and the optical density at λ _max (OD _max ) are as follows.

UV absorbers λ _max OD _max CGL 362 355 nm 1.23

Example D2 :

의 마젠타 발색제(M-9)를 포함하는 젤라틴 피복물로 피복한다. 젤라틴 피복물은 다음과 같은 성분을 포함한다(기재 물질 1㎡당 함량임).Polyethylene coated base materials, silver bromide and chemical formula

It is coated with a gelatin coating containing a magenta colorant (M-9). The gelatinous coating includes the following components (content per m 2 of the base material):

ingredient AgBr coating Gelatin Curing Agent Wetting Agent Silver Bromide Magenta Coloring Agent Tricresyl Phosphate 5.15 g 300 mg 85 mg 260 mg 325 mg 162 mg

The curing agent used is the potassium salt of 2,4-dichloro-6-hydroxytriazine, and the wetting agent used is the sodium salt of diisobutylniphthalenesulfonic acid.

Step wedges having a density difference of 0.3 log E per step are exposed on the resulting samples and then processed by Agfa Gevaert's P94 processing method for color negative paper according to the manufacturer's instructions.

After exposure and processing, the reflectance density in the green part is measured at a density of 0.9 to 1.1 of the wedge.

On a transparent base material as described in Example 1, a gelatin comprising the product of Example A1 is prepared. A control layer containing no UV absorbers is prepared in the same way.

Subsequently, in an Atlas exposure instrument, the magenta step wedge is exposed behind the product containing layer and the control layer of Example A1 (15 kJ / cm 2) and the reflectance density is measured again. With the CGL 362 layer, the magenta dye density loss (-ΔD) is significantly reduced compared to the control layer.

Example D3 :

The photo material which has the following layer structure is manufactured.

Top layer Red sensitive layer Second gelatin insertion layer Green sensitive layer First gelatin insertion layer Blue sensitive layer Polyethylene base

The gelatin layer consists of the following components (content per m 2 of the base material).

Blue sensitive layer

α- (3-benzyl-4-ethoxyhydantoin-1-yl) -α-pivaloyl-2-chloro-5- [α- (2,4-di-tamylphenoxy) butanamido] Acetanilide (400 mg)

α- (1-butylphenylurazol-4-yl) -α-pivaloyl-5- (3-dodecanesulfonyl-2-methylpropaneamido) -2-methoxyacetamide (400 mg)

Dibutyl phthalate (130mg)

Dinonyl Phthalate (130mg)

Gelatin (1200mg)

1,5-dioxa-3-ethyl-3- [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] -8,10-diphenyl-9-thia [ 5.5] Spirudecane (150 mg)

Bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate ( 150 mg)

3,5-di-t-butyl-4-hydroxy (2,4-di-t-amylphenyl) benzoate (150 mg)

Poly (N-t-butylacrylamide) (50 mg)

Blue Sensitive Silver Chlorobromide Emulsion (240mg)

First gelatin Insertion layer

Gelatin (1000mg)

2,5-di-t-octylhydroquinone (100 mg)

Hexyl 5- [2,5-dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoate (100 mg)

Dibutyl phthalate (200mg)

Diisodecyl Phthalate (200mg)

Green sensitive layer

7-chloro-2- {2- [2- (2,4-di-t-amylphenoxy) octanamido] -1-methylethyl} -6-methyl-1H-pyrazolo [1,5- b] [1,2,4] triazole (100 mg)

6-t-butyl-7-chloro-3- (3-dodecanesulfonylpropyl) -1H-pyrazolo [5,1-o] [1,2,4] triazole (100 mg)

Dibutyl phthalate (100mg)

Dicresyl Phosphate (100mg)

Trioctyl phosphate (100 mg)

Gelatin (1400mg)

3,3,3 ', 3'-tetramethyl-5,5', 6,6'-tetrapropoxy-1,1'-spirobiindane (100 mg)

4- (i-tridecyloxyphenyl) thiomorpholine 1,1-dioxide (100mg)

4,4'-butylidenebis (3-methyl-6-t-butylphenol) (50 mg)

2,2'-isobutylidenebis (4,6-dimethylphenol) (10 mg)

3,5-dichloro-4- (hexadecyloxycarbonyloxy) ethylbenzoate (20 mg)

3,5-bis [3- (2,4-di-t-amylphenoxy) propylcarbamoyl] sodium benzenesulfinate (20 mg)

Green Sensitive Silver Chlorobromide Emulsion (150mg)

Secondary gelatin Insertion layer

Gelatin (1000mg)

5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) benzo-1,2,3-triazole (200 mg)

2- (3-dodecyl-2-hydroxy-5-methylphenyl) benzo-1,2,3-triazole (200 mg)

Trinonyl Phosphate (300mg)

2,5-di-t-octylhydroquinone (50 mg)

Hexyl 5- [2,5-dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoate (50 mg)

Red sensitive layer

2- [α- (2,4-di-t-amylphenoxy) butanamido] -4,6-di-chloro-5-ethylphenol (150 mg)

2,4-dichloro-3-ethyl-6-hexadecaneamidophenol (150 mg)

4-chloro-2- (1,2,3,4,5-pentafluorobenzamido) -5- [2- (2,4-di-t-amylphenoxy) -3-methyl-butaneami Phenol (100 mg)

Dioctyl phthalate (100mg)

Dicyclohexyl phthalate (100mg)

Gelatin (1200mg)

5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) benzo-1,2,3-triazole (100 mg)

2- (3-dodecyl-2-hydroxy-5-methylphenyl) benzo-1,2,3-triazole (100 mg)

3,5-di-t-butyl-4-hydroxy (2,4-di-t-amylphenyl) benzoate (50 mg)

Poly (N-t-butylacrylamide) (300 mg)

N, N-diethyl-2,4-di-t-amylphenoxyacetamide (100 mg)

2,5-di-t-octylhydroquinone (50 mg)

Red Sensitive Silver Chlorobromide Emulsion (200mg)

The top layer containing the UV absorber and the top layer containing no UV absorber are prepared.

UV  Top layer containing absorbent

2,5-di-t-octylhydroquinone (20 mg)

Hexyl 5- [2,5-dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoate (20 mg)

Gelatin (400mg)

Trinonyl phosphate (120 mg)

UV absorbers: product of Example A1 (385 mg / activity)

UV  Top layer without absorbent

Gelatin (800mg)

The curing agent used is a 2,4-dichloro-6-hydroxytriazine potassium salt solution, and the wetting agent used is the sodium salt of diisobutylniphthalenesulfonic acid.

Three step wedges having a density difference of 0.3 log E per step are exposed on each sample (exposed with blue light, green light and red light, respectively). Subsequently, the method RA-4 of the Kodak for color paper is performed.

After exposure and processing, the reflectance densities in the red portions on the cyan stem, the green portions on the magenta step and the blue portions on the yellow step are measured at a density of 0.9 to 1.1 of the wedge. These wedges are then exposed (15 kJ / cm 2) in an Atlas exposure instrument and the reflectance density is measured again.

In the case of magenta wedges, the reflectance density before and after exposure is measured in the blue portion against yellow.

The presence of the product of Example A1 reduces the dye density loss of the cyan, magenta and yellow image dyes.

Claims (23)

A concentrated aqueous polymer dispersion having an average particle size of less than 1000 nm comprising a polymer carrier prepared by heterophasic radical polymerization of at least one ethylenically unsaturated monomer in the presence of a non-polar organic light stabilizer (b); A concentrated aqueous polymer dispersion wherein the weight ratio of nonpolar organic light stabilizer to polymer carrier exceeds 50 parts of light stabilizer per 100 parts of polymer carrier. The concentrated aqueous polymer dispersion of claim 1, further comprising a nonpolar, cationic or anionic surfactant. The concentrated aqueous polymer dispersion of claim 1, wherein the weight ratio of nonpolar organic light stabilizer to polymer carrier exceeds 80 parts of light stabilizer per 100 parts of carrier. The concentrated aqueous polymer dispersion of claim 1, wherein the average particle size is less than 500 nm. The non-polar organic light stabilizer of claim 1 is a hydroxyphenyl benzotriazole UV absorber, hydroxyphenyl triazine UV absorber, hydroxybenzophenone UV absorber, oxalic acid aniline UV absorber, sterically hindered amine light stabilizer and mixtures thereof A concentrated aqueous polymer dispersion, selected from the group consisting of: The concentrated aqueous polymer dispersion according to claim 1, wherein the water solubility of the nonpolar organic light stabilizer is less than 1% by weight at room temperature and atmospheric pressure. The method of claim 1 wherein the ethylenically unsaturated monomer is C ₁ -C ₁₈ acrylate, C ₁ -C ₁₈ methacrylate, acrylic acid, (meth) acrylic acid, styrene, vinyltoluene, hydroxy-functional acrylate or (meth Concentrated aqueous polymer dispersion, selected from the group consisting of acrylates, acrylates derived from alkoxylated alcohols, or (meth) acrylates, polyfunctional acrylates or (meth) acrylates, and mixtures thereof. 6. The compound of claim 5, wherein hydroxybenzophenone is a compound of formula I, 2-hydroxyphenylbenzotriazole is a compound of formula IIa, IIb or IIc, 2-hydroxyphenyltriazine is a compound of formula III, oxa A concentrated aqueous polymer dispersion wherein the nilide is a compound of Formula IV. Formula I

In Formula I above, v is an integer from 1 to 3, w is 1 or 2, Substituent Z is independently of each other hydrogen, halogen, hydroxyl or alkoxy having 1 to 12 carbon atoms. Formula IIa

In Formula IIa above, R ₁ is hydrogen, alkyl having 1 to 24 carbon atoms, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, cycloalkyl having 5 to 8 carbon atoms, or

Radicals {where R ₄ And R ₅ , independently of one another, are alkyl of 1 to 5 carbon atoms, or R ₄ together with the radicals C _n H _{2n + 1-m} form a cycloalkyl radical of 5 to 12 carbon atoms, m is 1 or 2 And n is an integer from 2 to 20, M is a radical of the formula -COOR ₆ , wherein R ₆ is hydrogen, alkyl of 1 to 12 carbon atoms, alkoxyalkyl of 1 to 20 carbon atoms, or alkyl moiety in the alkoxy moiety Phenylalkyl having 1 to 4 carbon atoms in R ₂ is hydrogen, halogen, alkyl having 1 to 18 carbons, and phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, R ₃ is hydrogen, chlorine, alkyl or alkoxy having 1 to 4 carbon atoms, or -COOR ₆ , wherein R ₆ is as defined above, At least one of the radicals R ₁ and R ₂ is not hydrogen. Formula IIb

In Formula IIb above, T is hydrogen or alkyl of 1 to 6 carbon atoms, T ₁ is hydrogen, chlorine or alkyl or alkoxy having 1 to 4 carbon atoms, n is 1 or 2, When n is 1, T ₂ is chlorine or the formula -OT ₃ or

Radicals wherein T ₃ is one or several times hydrogen, unsubstituted or substituted with 1 to 3 hydroxyl groups or alkyl having 1 to 18 carbon atoms, -O- or -NT ₆ -substituted by -OCOT ₆ Unsubstituted or substituted or substituted by hydroxyl or -OCOT ₆ alkyl of 3 to 18 carbon atoms, unsubstituted or substituted by hydroxyl and / or alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, unsubstituted Or alkenyl having 2 to 18 carbon atoms substituted by hydroxyl, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, or is of the formula -CH ₂ CH (OH) -T ₇ or

And T ₄ and T ₅ are independently of each other hydrogen; Alkyl having 1 to 18 carbon atoms; Alkyl having 3 to 18 carbons, interrupted once or several times by -O- or -NT _6- , cycloalkyl having 5 to 12 carbon atoms, phenyl, phenyl substituted by alkyl having 1 to 4 carbon atoms, 3 to 8 carbon atoms Alkenyl, phenylalkyl of 1 to 4 carbon atoms, or hydroxyalkyl of 2 to 4 carbon atoms, wherein T ₆ is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, or 3 to 3 carbon atoms Alkenyl of 8, phenyl, phenyl substituted by alkyl of 1 to 4 carbon atoms, phenylalkyl of 1 to 4 carbon atoms in the alkyl moiety, T ₇ is hydrogen, alkyl of 1 to 18 carbon atoms, unsubstituted or hydroxyl Substituted phenyl, phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, or -CH ₂ OT ₈ , T ₈ is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, phenyl Substituted by alkyl having 1 to 4 carbon atoms Phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety), When n is 2, T ₂ is a chemical formula

Or a radical of -OT ₉ -O- wherein T ₆ is as defined above and T ₁₀ is alkylene or cyclohexylene of 2 to 20 carbon atoms which may be blocked once or several times by -O-, T ₁₀ and T ₆ together with two nitrogen atoms are piperazine rings, T ₉ is alkylene of 2 to 8 carbon atoms, alkenylene of 4 to 8 carbon atoms, alkynylene of 4 carbon atoms, cyclohexylene, -O Alkylene of 2 to 8 carbon atoms blocked once or several times by-or -CH ₂ CH (OH) CH ₂ 0T ₁₁ OCH ₂ CH (OH) CH ₂ -or -CH ₂ -C (CH ₂ 0H ) ₂ -CH ₂ -radical, wherein T ₁₁ is alkylene having 2 to 8 carbon atoms, alkylene having 2 to 18 carbon atoms interrupted once or several times by -O-, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,3-phenylene or 1,4-phenylene). Formula IIc

In Formula IIc above, R ' ₂ is C ₁ -C ₁₂ alkyl, k is a number from 1 to 4. Formula III

In Formula III above, u is 1 or 2, r is an integer of 1 to 3, Substituent Y ₁ is Independently of each other, hydrogen, hydroxyl, phenyl or halogen, halogenomethyl, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 18 carbon atoms, or 1 to 18 carbon atoms substituted by -COO (C ₁ -C ₁₈ alkyl) Is alkoxy, when u is 1, Y ₂ is alkyl having 1 to 18 carbon atoms; Phenyl unsubstituted or substituted by hydroxyl, halogen, alkyl or alkoxy having 1 to 18 carbon atoms; Substituted by -COOH, -COOY ₈ , -CONH ₂ , -CONHY ₉ , -CONY ₉ Y ₁₀ , -NH ₂ , -NHY ₉ , -NY ₉ Y ₁₀ , -NHCOY ₁₁ , -CN and / or -OCOY ₁₁ Alkyl having 1 to 12 carbon atoms; Alkyl of 4 to 20 carbon atoms, interrupted by one or more oxygen atoms, unsubstituted or substituted by hydroxyl or alkoxy having 1 to 12 carbon atoms; Alkenyl having 3 to 6 carbon atoms; Glycidyl; Cyclohexyl unsubstituted or substituted by hydroxyl, alkyl of 1 to 4 carbon atoms and / or -OCOY ₁₁ ; Phenylalkyl of 1 to 5 carbon atoms in the alkyl moiety which is unsubstituted or substituted by hydroxyl, chlorine and / or methyl, -COY ₁₂ or -SO ₂ Y ₁₃ , wherein Y ₈ is alkyl of 1 to 18 carbon atoms; Alkenyl having 3 to 18 carbon atoms; Alkyl of 3 to 20 carbon atoms interrupted by one or more oxygen atoms or sulfur atoms or -NT ₆ -and / or substituted by hydroxyl; Alkyl having 1 to 4 carbon atoms substituted by —P (O) (OY ₁₄ ) ₂ , —NY ₉ Y ₁₀ or —OCOY ₁₁ and / or hydroxyl, wherein Y ₁₄ is alkyl or phenyl having 1 to 12 carbon atoms ); Alkenyl having 3 to 18 carbon atoms; Glycidyl; Or phenylalkyl having 1 to 5 carbon atoms in the alkyl moiety, and Y ₉ and Y ₁₀ are independently of each other alkyl having 1 to 12 carbon atoms, alkoxyalkyl having 3 to 12 carbon atoms, dialkylaminoalkyl having 4 to 16 carbon atoms or carbon atoms; Cyclohexyl of 5 to 12, or Y ₉ and Y ₁₀ are in each case alkylene, oxaalkylidene or azaalkylidene of 3 to 9 carbon atoms, Y ₁₁ is alkyl of 1 to 18 carbon atoms, al to 2 to 18 carbon atoms Or is phenyl, Y ₁₂ is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, phenyl, alkoxy having 1 to 12 carbon atoms, phenoxy, alkylamino having 1 to 12 carbon atoms, or phenylamino, and Y ₁₃ is alkyl, phenyl having 1 to 18 carbon atoms, or alkylphenyl having 1 to 8 carbon atoms in the alkyl radical; when u is 2, Y ₂ is interrupted by alkylene of 2 to 16 carbon atoms, alkenylene of 4 to 12 carbon atoms, xylylene, or one or more -O- and / or hydroxyl, -CH ₂ CH (OH) CH ₂ -OY ₁₅ -OCH ₂ CH (OH) CH ₂ , -CO-Y ₁₆ -CO-, -CO-NH-Y ₁₇ -NH-CO- or-(CH ₂ ) _m -CO ₂ -Y _18- Alkylene having 3 to 20 carbon atoms substituted by OCO- (CH ₂ ) _m , wherein m is 1, 2 or 3, and Y ₁₅ is alkylene, phenylene, or -phenylene-M having 2 to 10 carbon atoms -Phenylene-, wherein M is -O-, -S-, -S0 _2- , -CH ₂ -or -C (CH ₃ ) _2- ; and Y ₁₆ is in each case 2 to 10 carbon atoms Alkylidene, oxaalkylidene or thiaalkylidene of; Phenylene; Or alkenylene having 2 to 6 carbon atoms, Y ₁₇ is alkylene having 2 to 10 carbon atoms; Phenylene; Or alkylphenylene having 2 to 11 carbon atoms in the alkyl residue, Y ₁₈ is alkylene having 2 to 10 carbon atoms; Or alkylene having 4 to 20 carbon atoms interrupted once or several times by oxygen. Formula IV

In Formula IV above, x is an integer from 1 to 3, Substituents L , independently of each other, are hydrogen; In each case, alkyl, alkoxy or alkylthio having 1 to 22 carbon atoms; Phenoxy or phenylthio. 6. The sterically hindered amine of claim 5, wherein the sterically hindered amine is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl ) Succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperi Dill) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1 Condensate of-(2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis (2,2,6,6-tetra Straight or cyclic condensates of methyl-4-piperidyl) hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6 , 6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate , 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetra Tilpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2 -(2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5 ] Decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis- (2,2,6,6-tetra Linear or cyclic condensates of methyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis ( Condensate of 4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2-chloro -4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-amino Condensate of propylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] -decane-2,4-dione, 3 -Dodecyl-1- (2,2,6,6-tetramethyl-4-pipe Lidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4 A mixture of -hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetramethyl-4-pi Condensed product of hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6 Condensation product of -trichloro-1,3,5-triazine with 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No. 136504-96-6), N- (2,2 , 6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecyl Succinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, 7,7,9,9 Tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4,5] decane and epichlorohydrin reaction product, 1,1-bis (1,2, 2,6,6-pentamethyl-4-pipe Dyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) Hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane with 2,2,6,6-tetramethyl-4-aminopiperidine of maleic anhydride-α-olefin-copolymer Reaction product of 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethyl Piperidin-4-yl) -N-butyl-amino] -6- (2-hydroxyethyl) -amino-1,3,5-triazine, 1- (2-hydroxy-2-methylpropoxy ) -4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine, 5- (2-ethylhexanol) oxymethyl-3,3,5-trimethyl-2-morpholinone and Chemical formula

A concentrated aqueous polymer dispersion, selected from the group consisting of: wherein n is 1 to 15. A process for preparing a concentrated aqueous polymer dispersion having an average particle size of less than 1000 nm comprising the step of heterophasic radical polymerization of at least one ethylenically unsaturated monomer in the presence of a nonpolar organic light stabilizer, A process for producing a concentrated aqueous polymer dispersion wherein the weight ratio of nonpolar organic light stabilizer to polymer carrier made from ethylenically unsaturated monomers exceeds 50 parts of light stabilizer per 100 parts of polymer carrier. The method of claim 10, Dissolving, emulsifying or dispersing the nonpolar organic light stabilizer in at least one ethylenically unsaturated monomer (a), (B) preparing a conventional oil-in-water emulsion consisting of a light stabilizer dissolved, emulsified or dispersed in at least one ethylenically unsaturated monomer, (C) homogenizing a conventional emulsion into a miniemulsion having an average diameter of organic phase droplets of less than 1000 nm and A process for preparing a concentrated aqueous polymer dispersion comprising the step (d) of adding a polymerization initiator to polymerize a miniemulsion, A process for producing a concentrated aqueous polymer dispersion wherein the weight ratio of nonpolar organic light stabilizer to polymer carrier produced from ethylenically unsaturated monomers exceeds 50 parts of light stabilizer per 100 parts of polymer carrier. A polymer powder obtainable by volatilizing the volatile components of the concentrated aqueous polymer dispersion according to claim 1.  Stabilized against degradation induced by heat, oxidation or light, comprising an organic material (a) susceptible to degradation induced by heat, oxidation or light and a concentrated aqueous polymer dispersion (b) according to claim 1 Composition. The composition of claim 13, wherein the amount of component (b) is 0.1 to 40 percent by weight based on the weight of the solid component of component (a). The composition of claim 13, wherein the organic material is a recording material and stabilized against degradation induced by heat, oxidation or light. 16. The composition as claimed in claim 15, wherein the recording material is a photographic material or an inkjet material. 16. The composition of claim 15, wherein the recording material is a printing material containing a concentrated aqueous polymer dispersion-containing printing material in an overprint varnish. The composition of claim 13, wherein the organic material is an adhesive, an aqueous emulsion of natural or synthetic rubber, an aqueous ink or an aqueous coating, wherein the composition is stabilized against degradation induced by heat, oxidation or light. 19. The composition of claim 18, wherein component (a) is an aqueous coating, stabilized against degradation induced by heat, oxidation or light. A powder coating composition stabilized against degradation induced by heat, oxidation or light, comprising a solid binder material (a) and a polymer powder (b) according to claim 12. A composition stabilized against degradation induced by heat, oxidation or light, comprising a thermoplastic polymer (a) and a polymer powder (b) according to claim 12. Use of the concentrated aqueous polymer dispersion according to claim 1 as a stabilizer against heat, oxidation or light induced degradation of organic materials susceptible to degradation induced from heat, oxidation or light. Use of the polymer powder according to claim 12 as a stabilizer against deterioration induced by heat, oxidation or light of the powder coating.